Author: "Françoise Robin-le Guen" - Searchworks@Jio Institute Digital Library Search Results

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1. A comprehensive study of tetracyanobutadiene push-pull chromophores derived from γ-pyranylidene

Author: Clotilde Philippe, Johann Melan, Alberto Barsella, Thomas Vives, Yann R. Leroux, Françoise Robin-Le Guen, Loïc Lemiègre, Denis Jacquemin, Sébastien Gauthier, and Yann Trolez
Subjects: γ-Pyranylidene, TCBD, Cycloaddition-retroelectrocyclization, Nonlinear optics, Organic chemistry, QD241-441
Abstract: A new class of push-pull 1,1,4,4-tetracyanobutadienes (TCBDs) chromophores bearing a γ-pyranylidene as a pro-aromatic donor group have been developed, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. [2 + 2] Cycloaddition-retroelectrocyclizations (CA-RE) with tetracyanoethylene (TCNE) allowed the formation of new TCBDs by taking advantage of the electron-donating ability of γ-pyranylidene functional groups. The limits of the reaction between TCNE and the corresponding alkynes have been investigated, both in terms of reactivity and solubility. Electrochemical studies of pyranylidene-TCBD 1a-1j revealed two reversible reduction waves typical of TCBDs, and two oxidation waves originating from the γ-pyranylidene moiety. More complex electrochemical signals have been recorded when studying chromophores bearing multiple TCBD and/or γ-pyranylidene units. All pyranylidene-TCBDs showed panchromatic absorption properties, extending to the NIR in some cases. Changes made around the electron-withdrawing TCBD units significantly affected the ICT performance of the push-pull chromophores. Computational studies have been performed on this series of compounds to rationalize the origin of their optical properties. TD-DFT calculations confirmed that the synthesized pyranylidene-TCBDs are potential NLOphores. The second-order NLO properties of all chromophores were determined by the Electric Field-Induced Second Harmonic generation (EFISH) technique, and all systems exhibited valuable NLO properties with large μβEFISH values for purely organic compounds, up to 5700 10−48 esu.
Published: 2023
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2. 4,6-Bis((E)-2-(4′-N,N-diphenylamino-[1,1′-biphenyl]-4-yl)vinyl)-2-phenylpyrimidine

Author: Lacina Diarra, Françoise Robin-le Guen, and Sylvain Achelle
Subjects: pyrimidine, fluorescence, push–pull, Inorganic chemistry, QD146-197
Abstract: In this contribution, we designed a 4,6-distyrylpyrimidine chromophore with diphenylamino electron-donating groups and biphenylenevinylene extended π-conjugated linkers. This compound has been synthesized in two steps from 4,6-dimethyl-2-phenylpyrimidine by a double Knoevenagel reaction with 4-bromobenzaldehyde followed by a double Suzuki–Miyaura cross coupling reaction with 4-(N,N-diphenylamino)phenylboronic acid. This compound exhibits intense emission in moderately polar solvents as well as in solid state. This compound is characterized by an intense emission solvatochromism with emission ranging from blue in non polar n-heptane to orange in dichloromethane. This chromophore is also sensible to the presence of acid with a bathochromic shift of the charge transfer absorption band and emission quenching.
Published: 2021
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3. Carbazole- and Triphenylamine-Substituted Pyrimidines: Synthesis and Photophysical Properties

Author: Sylvain Achelle, Julián Rodríguez-López, Massinissa Larbani, Rodrigo Plaza-Pedroche, and Françoise Robin-le Guen
Subjects: pyrimidines, fluorescence, white-light emission, intramolecular charge transfer, Organic chemistry, QD241-441
Abstract: A series of pyrimidine derivatives bearing one, two or three triphenylamine/9-ethylcarbazole substituents has been synthesized by Suzuki cross-coupling reaction. All compounds showed absorption bands in the UV region and the emission of violet-blue light upon irradiation. Protonation led to quenching of the fluorescence, although some derivatives remained luminescent with the appearance of a new red-shifted band in the spectra. Accurate control of the amount of acid enabled white photoluminescence to be obtained both in solution and in solid state.
Published: 2019
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4. The arylvinylpyrimidine scaffold: a tunable platform for luminescent and optical materials

Author: Sylvain Achelle, Julián Rodríguez-López, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM), and Funding from the Junta de Comunidades de Castilla-La Mancha/FEDER is gratefully acknowledged by S. A. and J. R.-L. (project SBPLY/21/180501/000042).
Subjects: Organic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Biochemistry
Abstract: International audience; The incorporation of electron-withdrawing pyrimidine rings within π-extended systems allows access to a wide variety of fluorescent push-pull molecules that display emission properties highly sensitive to external stimuli. A suitable design of these compounds leads to interesting materials for a variety of optoelectronic applications. In this context, a vast number of arylvinylpyrimidine-based chromophores have been extensively studied during the last two decades. Along with the main synthetic pathways, this review summarizes the photophysical features of these active compounds having great potential and their most important applications as sensors and luminescence materials.
Published: 2023
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5. Phosphorescent cyclometalated platinum( ii ) complexes with phenyldiazine N^C ligands

Author: Mariia Hruzd, Samia Kahlal, Nicolas le Poul, Laurianne Wojcik, Marie Cordier, Jean-Yves Saillard, Julián Rodríguez-López, Françoise Robin-le Guen, Sébastien Gauthier, Sylvain Achelle, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM), and M. H. acknowledges the Région Bretagne, France and Conseil Départemental des Côtes d'Armor, France for her PhD funding (MMLum project).
Subjects: Inorganic Chemistry, expert elicitation, Chemical risk assessment chemical risk matrix expert elicitation real work situation, real work situation, Chemical risk assessment, chemical risk matrix, [CHIM]Chemical Sciences
Abstract: International audience; A series of phosphorescent platinum(II) complexes containing various phenyldiazine-type bidentate N^C ligands have been successfully synthesized and characterized. Structural modifications have been made to bidentate cyclometalating ligands regarding the nature of the diazine ring (pyrimidine, pyrazine and quinazoline), the substituent groups at the C4 position of the pyrimidine ring (OCH3, CF3) and the EDGs at the para position of the Pt atom (OCH3, Ph, NPh2, carbazol). In addition, the electronic properties of the azaheterocyclic ancillary ligand have been modulated in this series of complexes (pyridine, 4-methoxy-pyridine or pyrimidine). X-ray diffraction studies have been performed on three complexes, revealing Pt(II) ions in a distorted square-planar geometrical environment with no Pt(II)⋯Pt(II) interactions but with moderate π–π interactions in the solid-state structure. Electrochemical and computational studies suggest a ligand-centered reduction on the diazine ligands with, in some cases, additional contribution from the azaheterocyclic ancillary ligand, whereas oxidation occurs on the Pt-phenyl ring substituent moieties. All complexes exhibit phosphorescence emission ranging from green to red/near-infrared, both in solution and in the solid state. Complexes bearing a 2-(3-methoxyphenyl)pyrimidine ligand show the best PLQY of the series, up to 52% in a CH2Cl2 solution and 20% in the solid state. Furthermore, the solid state PLQY of one of the near-infrared emitting phenylquinazoline complex has been found to be 6%.
Published: 2023
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6. Cyclometallated 2‐Phenylpyrimidine Derived Platinum Complexes: Synthesis and Photophysical Properties

Author: Samia Kahlal, Julien Boixel, Sylvain Achelle, Thierry Roisnel, Françoise Robin-le Guen, Jean-Yves Saillard, Mariia Hruzd, Sébastien Gauthier, Michaela Fecková, Filip Bureš, Pascal Le Poul, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University of Pardubice, France Region Bretagne, Conseil Departemental des Cotes d'Armor, France, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Phosphorescence, 010405 organic chemistry, Chemistry, Ligand, Substituent, chemistry.chemical_element, Heterocycles, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Ring (chemistry), 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, N ligands, Pyrimidine, Absorption band, Pyridine, Platinum (II) complexes, [CHIM]Chemical Sciences, Platinum, HOMO/LUMO
Abstract: International audience; A series of five platinum (II) complexes based on 2-phenylpyrimidine ligands have been designed. Pyridine and chloride were used as auxiliary ligands. These complexes exhibit a slightly distorted square-planar geometry. The nature and position of substituent on the phenyl ring was thoroughly studied. The presence of an electron-donating substituent on the phenyl ring in the para position of the platinum atom leads to a red shift of the lowest-energy absorption band, which corresponds to the HOMO -> LUMO transition and permits to obtain phosphorescence in deoxygenated CH2Cl2 solution. All compounds are emissive in the solid state with a significant redshift for complexes bearing electron-donating substituent on the phenyl ring of phenylpyrimidine ligand.
Published: 2021
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7. Investigation of second-order nonlinear optical responses in a series of V-shaped binuclear platinum(<scp>ii</scp>) complexes

Author: Sébastien Gauthier, Denis Jacquemin, Françoise Robin-le Guen, Elsa Caytan, Sylvain Achelle, Raphaël J. Durand, Alberto Barsella, Nicolas Le Poul, Patricia Guevara Level, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Ministère de l'Enseignement supérieur, de la Recherche et de l'Innovation, Centre National de la Recherche Scientifique, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Series (mathematics), Pyrimidine, Ligand, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, [CHIM]Chemical Sciences, Order (group theory), Density functional theory, 0210 nano-technology, Platinum, Malononitrile
Abstract: International audience; A series of four D-(π-Pt-π-A)2 new V-shaped binuclear platinum(ii) complexes bearing a diphenylpyranylidene ligand as a pro-aromatic donor group (D) and various electron-attracting groups (A) separated by platinum bis-acetylide fragments have been synthesized, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. The nonlinear optical properties of these complexes have been determined by using the Electric-Field-Induced Second Harmonic (EFISH) generation technique, and their optical properties have been rationalized by Time-Dependent Density Functional Theory (TD-DFT) calculations relying on a range-separated hybrid. All complexes display positive μβ0 values. In addition, the second-order NLO responses of the complexes could be easily modulated by incorporating various end-capped electron-attracting groups, namely malononitrile, indane-1,3-dione, pyrimidine and pyrimidinium. Remarkably, complex 7 bearing a pyrimidinium fragment displays the highest μβ0 value among all the complexes of this series. Its NLO response is twice as high as that of the mononuclear analogue complex RD2, which has been confirmed both experimentally and theoretically.
Published: 2021
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8. Comparative studies of new pyranylidene-based sensitizers bearing single or double anchoring groups for dye-sensitized solar cells

Author: Mohammed Boujtita, Yann Pellegrin, Laurianne Wojcik, Sébastien Gauthier, Fabrice Odobel, Denis Jacquemin, Aurélien Planchat, Nicolas Le Poul, Patricia Guevara Level, Nadine Szuwarski, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We thank the Région des Pays de la Loire, for financial support via LUMOMAT program. This work used the computational resources of the CCIPL installed in Nantes, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Nantes - Faculté des Sciences et des Techniques, and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Anchoring dyes, 020209 energy, Substituent, γ-pyranylidene, Anchoring, Photovoltaic performance, Electron donor, 02 engineering and technology, Dye-sensitized solar cells, Electrochemistry, Photochemistry, 7. Clean energy, chemistry.chemical_compound, Substituent effect, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, TD-DFT calculations, 0202 electrical engineering, electronic engineering, information engineering, [CHIM]Chemical Sciences, Moiety, General Materials Science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Renewable Energy, Sustainability and the Environment, Photovoltaic system, Energy conversion efficiency, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dye-sensitized solar cell, chemistry, Single and double, 0210 nano-technology
Abstract: International audience; Mono- and di-anchoring γ-pyranylidene-based organic dyes featuring D–π–A and D–(π–A)2 architectures have been engineered as sensitizers for applications in Dye-Sensitized Solar Cells (DSSCs). Their photophysical, electrochemical and photovoltaic properties were further investigated. TD-DFT calculations were performed to rationalize the trends observed in the optical and electrochemical properties of the dyes. The investigation of the photovoltaic performances of this series of new dyes provided structure–property relationships where their Power Conversion Efficiencies (PCE) could be correlated to structural features, such as the length of the π-conjugated spacer, the nature of the substituents on the pyranylidene electron donor moiety and the number of anchoring groups. Dye-Sensitized Solar Cells based on mono-anchoring dyes were more efficient than the corresponding cells based on di-anchoring analogues due to high dye loading. The highest Power Conversion Efficiency of 5.23% was achieved with the mono-anchoring 17a dye containing t-butyl substituent groups on the pyranylidene fragment and with one thienyl π-conjugated spacer.
Published: 2020
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9. Luminescent cyclometalated alkynylplatinum(ii) complexes with 1,3-di(pyrimidin-2-yl)benzene ligands: synthesis, electrochemistry, photophysics and computational studies

Author: Mariia Hruzd, Nicolas le Poul, Marie Cordier, Samia Kahlal, Jean-Yves Saillard, Sylvain Achelle, Sébastien Gauthier, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Region Bretagne, France Region Bretagne, and Conseil Departemental des Cotes d'Armor, France
Subjects: Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract: International audience; In this article, we report on a series of cyclometalated chloro- and alkynyl-platinum(ii) complexes bearing various tridentate NCN-cyclometalated ligands derived from 1,3-bis(pyrimidin-2-yl)benzene. The X-ray crystal structures of two alkynyl-platinum(ii) complexes were determined and other structures were DFT-calculated. Electrochemical and DFT-computational studies suggest a ligand-centred reduction on the R-1-substituted NCN ligand, whereas oxidation likely occurs either on the Pt-phenylacetylide moiety and/or the cyclometalated ligand. In CH2Cl2 solution at room temperature, the complexes show phosphorescent emissions ranging from green to orange, depending on the R-1 and R-2 substituents on the ligands. In KBr solid state matrix, excluding complexes bearing a trifluoromethyl substituted ligand, all compounds exhibit red emission. The presence of an alkynyl ancillary ligand has limited influence on absorption and emission spectra except in the case of the complex with the strongly electron-donating diphenylamino R-2 substituent on the alkynyl ligand, for which a significant red-shift was observed. The alkynyl Pt(ii) complex with OMe groups as both R-1 and R-2 substituents shows the best emission quantum yield (0.81 in CH2Cl2 solution) in this series. The full series of DFT calculated band gaps correlated generally well with the electrochemical and absorption data and reasonably model the impact of the substituents on the electronics of these complexes.
Published: 2022
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10. Influence on photophysical properties of (de)protonation of phenol-substituted diazine chromophores: experimental and theoretical studies

Author: Maxime Hodée, Augustin Lenne, Julian Rodriguez-Lopez, Françoise Robin-Le Guen, Sylvain Achelle, Claudine Katan, Arnaud Fihey, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Instituto de Nanociencia, Nanotecnologia y Materiales Moleculares, Universidad de Castilla-La Mancha (INAMOL), Universidad de Castilla-La Mancha (UCLM), Calculations were performed at ISCR and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2021-A0100800649 made by Grand Equipement National de Calcul Intensif (GENCI)., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2021

11. V-Shaped Methylpyrimidinium Chromophores for Nonlinear Optics

Author: Alberto Barsella, Filip Bureš, Françoise Robin-le Guen, Sylvain Achelle, Michaela Fecková, Egor V. Verbitskiy, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Ural Federal University [Ekaterinburg] (UrFU), Institute of Organic Chemistry and Technology [University of Pardubice], University of Pardubice, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Russian Foundation for Basic Research. Grant Number: 18-29-23045, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Jonchère, Laurent
Subjects: Materials science, pyrimidines, donor-acceptor systems, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Electric field, [CHIM] Chemical Sciences, PYRIMIDINES, SECOND-ORDER NONLINEAR OPTICS, Figure of merit, chromophores, [CHIM]Chemical Sciences, DONOR-ACCEPTOR SYSTEMS, photophysics, Chloroform, 010405 organic chemistry, Nonlinear optics, Regioselectivity, Second-harmonic generation, General Chemistry, Chromophore, 0104 chemical sciences, Crystallography, Dipole, chemistry, CHROMOPHORES, second-order nonlinear optics, PHOTOPHYSICS
Abstract: A series of four V-shaped methylpyrimidinium salts bearing diphenylamino-electron-donating groups appended at various pyrimidine positions were designed. These chromophores were obtained by regioselective N(1) monomethylation by methyl methanesulfonate of the pyrimidine core. Linear optical properties were studied experimentally and electronic properties were further completed by (TD)-DFT calculations. The second-order nonlinear optical (NLO) properties were also studied using electric field induced second harmonic generation (EFISH) method in chloroform, and all pyrimidinium salts exhibited μβ0>1000×10−48 esu. The 2,4-disubstituted pyrimidinium core is preferred over 4,6-disubstitution as it enhances the NLO response and increases the dipole moment. (E,E)-2,4-Bis[4-(diphenylamino)styryl]-1-methylpyrimidin-1-ium methanesulfonate appears to be the best NLO-phore in chloroform in the series (μβ0=2500×10−48 esu) and a figure of merit μβ0/MW=3.4 10−48 esu mol g−1. © 2021 Wiley-VCH GmbH VEV is grateful for the financial support for the synthetic part related to compound 3 from the Russian Foundation for Basic Research (Research Project No. 18-29-23045 mk). MF acknowledges the Région Bretagne, France for her Ph.D. funding (HOLED project).
Published: 2021
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12. Effect of protonation on the photophysical properties of 4-substituted and 4,7-disubstituted quinazoline push-pull chromophores

Author: Arnaud Fihey, Claudine Katan, Françoise Robin-le Guen, Julián Rodríguez-López, Rodrigo Plaza-Pedroche, Sylvain Achelle, D. N. Georgiou, Mihalis Fakis, Facultad de Ciencias y Tecnologias Quimicas, Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM), University of Patras, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CTQ2017-84561-P, Ministerio de Economía y Competitividad, Agencia Estatal de Investigación, SBPLY/17/180501/000214, Junta de Comunidades de Castilla-La Mancha, Universidad de Castilla-La Mancha (UCLM), University of Patras [Patras], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Photoluminescence, Materials science, General Chemical Engineering, Protonation, 02 engineering and technology, 010402 general chemistry, Ring (chemistry), Photochemistry, 01 natural sciences, chemistry.chemical_compound, push-pull chromophores, White light, Quinazoline, quinazolines, Push pull, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Solvatochromism, white-light emission, Chromophore, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, fluorescence, 0210 nano-technology
Abstract: International audience; White-light emission from single molecular systems has attracted a great deal of attention due to their advantages over multicomponent emitters. Azaheterocyclic push-pull derivatives have been demonstrated to be white emitters by combining neutral and protonated forms in the appropriate ratio, although limited cases of white-light emission have been reported from quinazoline derivatives. Herein, we describe a series of push-pull 4-substituted and 4,7-disubstituted quinazolines that show white photoluminescence both in solution and in the solid state. All of the materials were prepared by straightforward Suzuki-Miyaura crosscoupling reactions and the compounds exhibited remarkable emission solvatochromism. In some cases the presence of acid prompted the appearance of emission bands of complementary colors. Thus, multicolor photoluminescence, including white light, could be finely tuned by the controlled protonation of the electron-deficient quinazoline ring.
Published: 2021
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13. N'N'C platinum (II) complexes based on phenyl-pyridin-2-ylpyrimidine ligands: synthesis, electrochemical and photophysical properties

Author: Sébastien Gauthier, Sylvain Achelle, Julien Boixel, Mariia Hruzd, Jean-Yves Saillard, Françoise Robin-le Guen, Nicolas Le Poul, Samia Kahlal, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), France Region Bretagne, Conseil Departemental des Cotes d'Armor, France, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: General Chemical Engineering, chemistry.chemical_element, Quantum yield, 010402 general chemistry, Excimer, Electrochemistry, 01 natural sciences, Alkynyl complexes, Metal, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 010405 organic chemistry, Phosphorescence, Process Chemistry and Technology, 0104 chemical sciences, Crystallography, chemistry, Pyrimidine, visual_art, visual_art.visual_art_medium, Platinum (II) complexes, N"N"C ligand, Density functional theory, Luminescence, Platinum
Abstract: International audience; A series of luminescent chloro- and alkynyl-platinum (II) complexes containing various tridentate cyclometalated ligands derived from phenyl-pyridin-2-ylpyrimidine and alkynyl ligands has been successfully synthesized and characterized. Their electrochemical, electronic absorption and luminescence properties have been experimentally investigated and supported by (Time-Dependent) Density Functional Theory ((TD)-DFT) calculations. Electrochemical studies show the presence of a ligand-centered reduction originating from the cyclometalating N"N"C ligands, as well as a major ligand-centered oxidation process (N"N"C or alkynyl) with minor contributions of the metal. Most of the complexes exhibits yellow-to-red luminescence at room-temperature in diluted solutions, in frozen matrices and in the solid state. Electron-withdrawing groups on the alkynyl-ligand induce a red shift of the emission band with increased quantum yield in solution. The emission is also sensitive to the position of the pyridyl fragment on the pyrimidine core: complexes with electron-poorer 4-pyridin-2-ylpyrimidine ligands exhibit red-shifted emission and decreased quantum yield compared to their 2-pyridin-4yl analogues. In solid state, chloro-platinum complexes without tBu bulky group exhibit red-shifted excimer emission.
Published: 2021
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14. Photophysics of 9,9-Dimethylacridan-Substituted Phenylstyrylpyrimidines Exhibiting Long-Lived Intramolecular Charge-Transfer Fluorescence and Aggregation-Induced Emission Characteristics

Author: Filip Bureš, Sylvain Achelle, Pascal Le Poul, Milan Klikar, Oldřich Pytela, Françoise Robin-le Guen, Thierry Roisnel, Michaela Fecková, Ioannis Konstantinos Kalis, Mihalis Fakis, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Patras, University of Pardubice, University of Patras, School of Medicine, HOLED, Région Bretagne, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and University of Patras [Patras]
Subjects: Dual emission, 010405 organic chemistry, Chemistry, Organic Chemistry, Solvatochromism, General Chemistry, Chromophore, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence, Catalysis, Aggregation induced emission, 0104 chemical sciences, Pyrimidine, Intramolecular force, Moiety, [CHIM]Chemical Sciences, Knoevenagel condensation, Intramolecular charge transfer, Spectroscopy, Visible spectrum
Abstract: International audience; Six pyrimidine-based push-pull systems substituted at positions C2 and C4/6 with phenylacridan and styryl moieties, employing methoxy or N,N-diphenylamino donors, have been designed and synthesized through cross-coupling and Knoevenagel reactions. X-ray analysis confirmed that the molecular structure featured the acridan moiety arranged perpendicularly to the residual π system. Photophysical studies revealed significant differences between the methoxy and N,N-diphenylamino chromophores. Solvatochromic studies revealed that the methoxy derivatives showed dual emission in polar solvents. Time-resolved spectroscopy revealed that the higher energy band involved very fast (
Published: 2020
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15. Influence of Donor-Substituents on Triphenylamine Chromophores Bearing Pyridine Fragments

Author: Oldřich Pytela, Julián Rodríguez-López, Michaela Fecková, Pascal Le Poul, Milan Klikar, Sylvain Achelle, Jiří Tydlitát, and Françoise Robin-le Guen
Subjects: Bearing (mechanical), 010405 organic chemistry, Organic Chemistry, Solvatochromism, Chromophore, 010402 general chemistry, Photochemistry, Triphenylamine, 01 natural sciences, Fluorescence, 0104 chemical sciences, law.invention, chemistry.chemical_compound, chemistry, law, Pyridine, Physical and Theoretical Chemistry
Published: 2019
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16. Tuning the Photophysical Properties of Push-Pull Azaheterocyclic Chromophores by Protonation: A Brief Overview of a French-Spanish-Czech Project

Author: Filip Bureš, Julián Rodríguez-López, Sylvain Achelle, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Universidad de Castilla-La Mancha (UCLM), University of Pardubice, Junta de Comunidades de Castilla-La Mancha, SBPLY/17/180501/000214, FEDER, Ministerio de Economía y Competitividad, Agencia Estatal de Investigación, CTQ2017-84561-P, FEDER, CZ.02.1.01/0.0/0.0/16_025/0007445, European Regional Development Fund-Project, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM)
Subjects: Photoluminescence, Materials science, 010405 organic chemistry, General Chemical Engineering, protonation, white-light emission, Nanotechnology, Protonation, General Chemistry, Chromophore, Conjugated system, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, 0104 chemical sciences, push-pull chromophores, photoluminescence, Materials Chemistry, OLED, Molecule, [CHIM]Chemical Sciences, nitrogen heterocycles, Luminescence
Abstract: International audience; Conjugated push-pull molecules that incorporate nitrogen heterocycles as electron-withdrawing units are interesting materials because of their luminescence properties. These chromophores can be easily and reversibly protonated at the nitrogen atom of the heterocyclic ring and this can cause dramatic color changes. White and multi-color photoluminescence both in solution and in the solid state can be obtained by an accurate control of the amount of acid. Thus, with a suitable design these compounds have potential applications in the development of colorimetric pH sensors and the fabrication of OLEDs based on only one material. We provide here a brief overview of our collaborative efforts made in this area.
Published: 2020
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17. Redox-switching of ternary Ni(<scp>ii</scp>) and Cu(<scp>ii</scp>) complexes: synthesis, experimental and theoretical studies along with second-order nonlinear optical properties

Author: Carolina Manzur, Françoise Robin-le Guen, Samia Kahlal, Jean-René Hamon, Jean-Yves Saillard, Thierry Roisnel, Isabelle Ledoux-Rak, Néstor Novoa, Nolwenn Cabon, Vincent Dorcet, David Carrillo, Universidad de Concepción [Chile], Pontificia Universidad Católica de Valparaíso (PUCV), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Fondo Nacional de Desarrollo Cientifico y Tecnologico [FONDECYT (Chile)] [1130105], Vicerrectoria de Investigacion y Estudios Avanzados, Pontificia Universidad Catolica de Valparaiso, Chile, CNRS, Universite de Rennes 1, GENCI French national computer center [a0050807367], CONICYT (Chile), BECAS-CHILE, Universidad de Concepción - University of Concepcion [Chile], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Schiff base, Ligand, Dimer, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Redox, Catalysis, Square pyramidal molecular geometry, 0104 chemical sciences, Metal, chemistry.chemical_compound, Crystallography, Nickel, chemistry, visual_art, Materials Chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, 0210 nano-technology, Ternary operation
Abstract: International audience; Four new ternary Ni(ii) and Cu(ii) complexes of ONO tridentate Schiff base and pyridylmethylenepyran (PyMP) ligands [(R-ONO)M(PyMP)] (R = anisyl = An M = Ni 1, Cu 2; R = ferrocenyl = Fc M = Ni 3, Cu 4) have been synthesized under facile reaction conditions starting from R-ONOH2, metal(ii) nitrate salts, and PyMP; R-ONOH2 stands for the Schiff base ligand precursors obtained by condensation of either 1-anisyl- or 1-ferrocenyl-butan-1,3-dione and 2-aminophenol. They have been thoroughly characterized with the help of various physicochemical tools, such as CHN analyses, IR and UV-vis spectra, H-1 NMR for diamagnetic Ni(ii) derivatives 1 and 3, and HRMS for paramagnetic Cu(ii) species 2 and 4. The molecular structures of 1-3 were authenticated by single-crystal X-ray diffraction methods, along with that of the doubly phenoxide-bridged dimer [Cu-2(mu-ONO-Fc)(2)(PyMp)(2)] (4 '), resulting from the recrystallization of 4. In 1-3, the four-coordinate nickel and copper atoms adopt a square planar geometry, whereas in 4 ' the Cu-II metal ion is five-coordinated in a square pyramidal environment with the pyridyl nitrogen occupying the apex. Electrochemical studies reveal two well-separated redox waves. The spin density distribution analyses reveal that the initial oxidation process is associated with a ligand-based level, with some ferrocenyl participation for the heterobimetallic compounds 3 and 4. Reversible redox switching can be established for 1 and 3 by time-resolved spectroelectrochemistry under thin-layer conditions where electrochemical cycling is associated with a significant modification of the UV-vis spectra of the chromophores. The second-order nonlinear optical responses of 1-4 along with those of assumed bispyrylium dimeric species 5 and 6, generated by chemical oxidation of 1 and 3, respectively, have been determined by harmonic light scattering measurements in dichloromethane solutions at 1.91 mu m incident wavelength. Rather high beta values ranging from 270-530 x 10(-30) esu were determined for 1-4. The beta value of 5 (800 x 10(-30) esu) was found to be almost twice that of its monomeric precursor 1, whereas the beta value of 6 (160 x 10(-30) esu) is reduced by half with respect to that of 3. In 5 the anisyl retains its donor ability whereas in 6 the electron-donating character of the oxidized ferrocenyl moiety is cancelled. Optimized geometries of the four compounds 1-4 as well as their electronic structures and that of their respective cations 1(+)-4(+) have been analyzed through DFT calculations, while TD-DFT computation has been used to interpret the major features of the UV-vis spectra.
Published: 2019
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18. Push-pull (iso)quinoline chromophores: synthesis, photophysical properties, and use for white light emission

Author: Sylvain Achelle, Arnaud Fihey, Zaina Ibrahim Mohamed Allaoui, Claudine Katan, Julián Rodríguez-López, Rodrigo Plaza-Pedroche, Françoise Robin-le Guen, Estelle le Gall, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de Technologie - Lannion (IUT Lannion), Université de Rennes (UR), Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM), J. R.-L. thanks the Ministerio de Economía y Competitividad/Agencia Estatal de Investigación/FEDER for financial support (project CTQ2017-84561-P). Funding from the Junta de Comunidades de Castilla-La Mancha/FEDER is also gratefully acknowledged by J. R.-L. and S. A. (project SBPLY/17/180501/000214)., Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), IUT de Lannion, Université de Rennes 1, Universidad de Castilla-La Mancha (UCLM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: push-pull chromophores π-bridge π-bridge D π-bridge (iso)quinoline, Astrophysics::High Energy Astrophysical Phenomena, Halochromism, (iso)quinolines, Protonation, Conjugated system, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Quinoline, Solvatochromism, white-light emission, General Chemistry, Chromophore, Fluorescence, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, fluorescence, Luminescence
Abstract: International audience; The photophysical properties of a series of conjugated push-pull (iso)quinolines were studied. The compounds were synthesized by well-established and straightforward methodologies. The materials exhibited not only emission solvatochromism in a variety of nonpolar solvents, but also tunable halochromism. Some of the compounds remained moderately luminescent after protonation and had a red emissive form, which was used to obtain white-light emission, both in solution and in thin films, by controlled protonation of the initially blue-green-emitting materials. This methodology has potential applications in the fabrication of white organic light-emitting diodes with two forms of a single emitter in equilibrium.
Published: 2020
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19. Push–pull D–π-Ru–π-A chromophores: synthesis and electrochemical, photophysical and second-order nonlinear optical properties

Author: Sébastien Gauthier, Françoise Robin-le Guen, Nicolas Le Poul, Samia Kahlal, Thomas Groizard, Alberto Barsella, Jean-Yves Saillard, Raphaël J. Durand, Sylvain Achelle, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: Materials science, Pyrimidine, chemistry.chemical_element, NLO, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, ruthenium complexes, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Second-harmonic generation, Non-linear optic, Chromophore, pyranylidene ligand, 0104 chemical sciences, Ruthenium, Crystallography, Dipole, chemistry, Intramolecular force
Abstract: The present work describes the one-pot synthesis and electrochemical, photophysical and second-order nonlinear optical (NLO) properties of a series of dipolar π-delocalized Ru(II) dialkynyl complexes. The eight new asymmetrical D–π-Ru–π-A push–pull chromophores incorporate pyranylidene ligands as pro-aromatic donor groups (D) and formaldehyde, indane-1,3-dione, pyrimidine or pyrimidinium as electron-attracting groups (A) separated by ruthenium bis-acetylide fragments and π-conjugated linkers. The second-order nonlinear optical (NLO) properties of all eight complexes were determined by the Electric-Field-Induced Second Harmonic generation (EFISH) technique (operating at 1907 nm), and were compared to those of their purely organic analogs. All investigated compounds (organic and organometallic) exhibited positive μβ values, which dramatically increased for the complexes due to the presence of ruthenium in the π-conjugated core. The second-order NLO response could also be easily modulated by changing the nature of alkynyl substituents. The most promising ruthenium complexes 7 and 8 of the series with the pyrimidinium fragment displayed μβ values of 14 000 × 10−48 esu. The effect of structural modifications on the redox and spectroscopic properties of the complexes was also studied. The intramolecular charge transfer (ICT) occurring through the ruthenium center of the push–pull σ-dialkynyl complexes was investigated by combining experimental and theoretical data.
Published: 2018
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20. Branching effect on the linear and nonlinear optical properties of styrylpyrimidines

Author: Françoise Robin-le Guen, Michaela Fecková, Claudine Katan, Mihalis Fakis, Fotis Kournoutas, Filip Bureš, Jean-Pierre Malval, Arnaud Fihey, Arnaud Spangenberg, Pascal Le Poul, Sylvain Achelle, University of Patras, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), University of Pardubice, HOLED, Région Bretagne, 2019-A0060800649, Grand Équipement National De Calcul Intensif, University of Patras [Patras], Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Département de Photochimie Générale (DPG), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), University Pardubice, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), and KATAN, Claudine
Subjects: Materials science, Absorption spectroscopy, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Physics and Astronomy, Electron, Chromophore, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, Triphenylamine, Branching (polymer chemistry), 01 natural sciences, Molecular physics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Polar effect, Molecule, Physical and Theoretical Chemistry, Time-resolved spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; This contribution aims at investigating the branching effect on the steady state, time resolved fluorescence and two-photon absorption (2PA) properties of dimethylamino and diphenylamino substituted styrylpyrimidine derivatives, by means of a combined experimental and theoretical study. In contrast to classical branched molecules with a triphenylamine central core and electron accepting groups at the periphery, here, branched molecules with reverse topology and different symmetries are examined, namely a styrylpyrimidine group is used as the electron withdrawing core and dimethylamino or diphenylamino donors are incorporated at the periphery. Besides, compared to the great majority of existing branched systems, the herein studied molecules do not have C3 symmetry. For this reason, the region of the linear and non-linear optical spectra of the two and three branched chromophores is actually similar. Interestingly, while the one-photon absorption spectra of one-branched systems versus two- or three-branched ones are spectrally shifted, there is almost no spectral shift in the main 2PA spectral region. Meanwhile, there is still an enhancement of both linear and nonlinear optical responses. Overall, here we developed a strategy that enhances the 2PA response while maintaining the spectral position. Specifically, 2PA cross section values as high as 500 GM have been obtained for the diphenylamino A–(π–D)3 molecule in dichloromethane.
Published: 2020
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21. Electron-Withdrawing Substituted Quinazoline Push-Pull Chromophores: Synthesis, Electrochemical, Photophysical and Second-Order Nonlinear Optical Properties

Author: Sylvain Achelle, Filip Bureš, Pascal Le Poul, Galina N. Lipunova, Tatiana N. Moshkina, Emiliya V. Nosova, Françoise Robin-le Guen, Alberto Barsella, Valery N. Charushin, Oldřich Pytela, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Ural Federal University [Ekaterinburg] (UrFU), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), University of Pardubice, Russian Academy of Sciences [Moscow] (RAS), Russian Foundation for Basic Research (RFBR) [18-03-00112, 19-33-90014], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Substituent, Second-harmonic generation, Quinazoline, Chromophore, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence, Push-pull derivatives, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Nonlinear chromophores, chemistry, Polar effect, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Cyclic voltammetry, Intramolecular charge transfer, Luminescence
Abstract: International audience; A series of chromophores bearing 4-cyanoquinazoline, 2-(4-cyanophenyl)quinazoline or 2-(4-trifluorophenyl)quinazoline electron-acceptor (A) and 5-(4-aminophenyl)thiophen-2-yl or 4-aminophenyl electron-donor (D) units has been designed. The influence of the electron-withdrawing substituent on the pyrimidine core as well as the nature of the amino electron donating group has been studied by cyclic voltammetry, UV/Vis and emission spectroscopy. Whereas 2-(4-cyanophenyl)quinazoline and 2-(4-trifluorophenyl)quinazoline derivatives are highly luminescent in chloroform solution, 4-cyanoquinazolines are poorly emissive. Interestingly all compounds are luminescent in the solid state with the emission ranging from blue to red. The second order nonlinear optical properties were studied using electric field induced second harmonic generation (EFISH) method. Quantum-chemical calculations corroborate the aforementioned experimental results.
Published: 2020
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22. Nonlinear optical properties of pyrimidine chromophores

Author: Michaela Fecková, Pascal Le Poul, Sylvain Achelle, Filip Bureš, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University of Pardubice, Conseil Régional de Bretagne, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Pyrimidine, business.industry, Process Chemistry and Technology, General Chemical Engineering, Nonlinear optic, Second-harmonic generation, 02 engineering and technology, Second harmonic generation, Chromophore, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Two-photon absorption, 0104 chemical sciences, chemistry.chemical_compound, Nonlinear optical, chemistry, Optoelectronics, [CHIM]Chemical Sciences, 0210 nano-technology, business
Abstract: International audience; The large library of nonlinear optical (NLO) chromophores based on pyrimidine scaffold is discussed in this review. Since the first examples described thirteen years ago, the interest in pyrimidine push-pull NLO chromophores has increased dramatically, especially for second harmonic generation and two photon absorption. More than 130 properly selected chromophores are presented to demonstrate fundamental structure-property relationships and to highlight key applications of pyrimidine-derived materials. © 2020 Elsevier Ltd
Published: 2020
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23. Synthesis and properties of novel pyranylidene-based organic sensitizers for dye-sensitized solar cells

Author: Patricia Guevara Level, Aurélien Planchat, Fabrice Odobel, Mohammed Boujtita, Laurianne Wojcik, Nicolas Le Poul, Sébastien Gauthier, Denis Jacquemin, Yann Pellegrin, Françoise Robin-le Guen, Nadine Szuwarski, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Nantes - Faculté des Sciences et des Techniques, and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, General Chemical Engineering, Substituent, chemistry.chemical_element, Electron donor, Photovoltaic performance, 02 engineering and technology, 010402 general chemistry, Photochemistry, Electrochemistry, Dye-sensitized solar cells, 01 natural sciences, 7. Clean energy, chemistry.chemical_compound, Substituent effect, Moiety, Organic sensitizers, [CHIM]Chemical Sciences, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Energy conversion efficiency, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dye-sensitized solar cell, chemistry, Density functional theory, 0210 nano-technology, TD-DFT, Carbon
Abstract: International audience; We report herein the synthesis of nine new molecularly engineered metal-free organic pyranylidene-based dyes as efficient photosensitizers for Dye-Sensitized Solar Cells (DSSCs). Their photophysical, electrochemical, and photovoltaic properties were investigated, and their excited states have been modelled using Time-Dependent Density Functional Theory (TD-DFT). The investigation of the photovoltaic performances of this series of new dyes provided structure-property relationships where their Power Conversion Efficiencies (PCE) could be correlated to structural features, such as the length of the π-conjugated spacer and the nature of the substituents on the upper (positions 2 and 6) and lower parts (substituents on the exocyclic carbon) of the pyranylidene electron donor moiety. While these dyes fulfilled the criteria of efficient sensitizers for TiO2-based DSSCs, their photovoltaic performances were found to depend on the dye packing arrangements controlled by substituents on the pyranylidene group. The highest Power Conversion Efficiency of 5.52% was reached with the 20a dye containing phenyl substituent groups in both upper and lower parts of the pyranylidene fragment and with one thienyl π-conjugated spacer. © 2019 Elsevier Ltd
Published: 2019
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24. Porosity-driven large amplitude dynamics for nitroaromatic sensing with fluorescent films of alternating D-π-A molecules

Author: Sylvain Achelle, Jean-Pierre Malval, Olivier Soppera, Yann Molard, M. Cranney, Françoise Robin-le Guen, Huriye Akdas-Kiliç, Nolwenn Cabon, Jean-Luc Fillaut, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Metals and Alloys, General Chemistry, Chromophore, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Amplitude, chemistry, Materials Chemistry, Ceramics and Composites, Molecule, Thin film, Porosity, Order of magnitude, Alkyl
Abstract: International audience; We report herein the structural properties and nitroaromatic sensing performances of fluorescent thin films formed by alternating donor-acceptor pi-conjugated chromophores. The incorporation of a flexible one-dimensional alkyl chain in the chromophore backbone drastically accelerates by more than one order of magnitude the sensing dynamics for the detection of 2,4-dinitrotoluene (DNT) vapors.
Published: 2019
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25. Synthesis and Photophysical Properties of Substituted Pyrimidines

Author: Sylvain Achelle, Julián Rodríguez-López, Massinissa Larbani, Rodrigo Plaza-Pedroche, and Françoise Robin-le Guen
Abstract: A series of pyrimidine derivatives bearing one, two or three triphenylamine/9-ethylcarbazole substituents has been synthesized by Suzuki cross-coupling reaction. All compounds showed absorption bands in the UV region and the emission of violet-blue light upon irradiation. Protonation led to quenching of the fluorescence, although some derivatives remained luminescent with the appearance of a new red-shifted band in the spectra. Accurate control of the amount of acid enabled white photoluminescence to be obtained both in solution and in solid state.
Published: 2019
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26. Synthesis and Photophysical Properties of a Series of Pyrazine-Based Push-Pull Chromophores

Author: Sébastien Gauthier, Raphaël J. Durand, Françoise Robin-le Guen, Kellyn M Hoffert, and Sylvain Achelle
Subjects: Pyrazine, 010405 organic chemistry, Chemistry, Organic Chemistry, Solvatochromism, Chromophore, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Intramolecular force, Polar, Knoevenagel condensation, Physical and Theoretical Chemistry, Absorption (chemistry), Push pull
Abstract: Eighteen push–pull pyrazine fluorophores are described. Methoxy, dimethylamino, and diphenylamino groups were used as electron-donating groups (EDGs), and six π-conjugated systems consisting of multiple bonds and 1,4-phenylene moieties were used to connect the EDGs to the pyrazine core. The chromophores were obtained by Knoevenagel condensation and palladium-catalyzed cross-coupling reactions starting from commercially available 2-methyl- or 2-chloropyrazine. The optical absorption and emission properties of these chromophores were studied in different solvents. Some proved to be highly emissive and exhibit strong emission solvatochromism, which suggests a highly polar emitting state, characteristic of compounds that undergo intramolecular charge transfer (ICT). The influences of the various electron-donating groups and π-conjugated systems on the emission and ICT have been carefully studied.
Published: 2016
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27. New 8-substituted BODIPY-based chromophores: synthesis, optical and electrochemical properties

Author: Bertrand Caro, Sébastien Gauthier, Françoise Robin-le Guen, Nikolay Vologdin, Sylvain Achelle, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), region Bretagne, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: aggregation-induced emission, intramolecular charge-transfer, boron dipyrromethene, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, Redox, chemistry.chemical_compound, energy-transfer, hg-ii, push-pull chromophores, [CHIM]Chemical Sciences, spectroscopic properties, photophysical properties, 010405 organic chemistry, Organic Chemistry, environmental polarity, Chromophore, Fluorescence, 0104 chemical sciences, solar-cells, chemistry, Absorption band, Polar effect, Cyclic voltammetry, BODIPY
Abstract: BODIPY-based chromophores, in which an electron withdrawing difluoro-boraindacene fragment is connected via position 8 to different donor fragments, were synthesized. Their electrochemical and photophysical properties were studied. All compounds exhibit a quasi-reversible oxidation corresponding to the formation of a BODIPY π-radical cation at around 0.8 V vs. FeCp2 +/FeCp2 that is slightly sensitive to the nature of the electron donating group. A reversible reduction is observed around−1.6 V vs. FeCp2 +/FeCp2 corresponding to the formation of the BODIPY π-radical anion. Cyclic voltammetry analysis of a γ-methylenepyran substituted BODIPY indicates the formation of redox bistable system with high bistability. In dichloromethane solution, the chromophores exhibit an intense absorption band around 502 nm and an emission in the 516–528 nm range. A significant emission quench is observed in case of amino and γ-methylenepyran substituents.
Published: 2016
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28. Synthesis, photophysical and nonlinear optical properties of [1,2,5]oxadiazolo[3,4-b]pyrazine-based linear push-pull systems

Author: Valery N. Charushin, Oleg N. Chupakhin, Filip Bureš, Yuriy A. Kvashnin, Sylvain Achelle, Gennady L. Rusinov, Pascal Le Poul, Egor V. Verbitskiy, Alberto Barsella, Françoise Robin-le Guen, Ural Federal University [Ekaterinburg] (UrFU), Ural Branch of Russian Academy of Sciences (UB RAS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Faculty of Chemical Technology [University of Pardubice], University of Pardubice, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Russian Foundation for Basic Research: 18-29-23045, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: Pyrazine, NONLINEAR OPTIC, General Chemical Engineering, DONOR–ACCEPTOR SYSTEMS, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, intramolecular charge transfer, 01 natural sciences, chemistry.chemical_compound, INTRAMOLECULAR CHARGE TRANSFER, Electric field, [CHIM]Chemical Sciences, Order (group theory), Emission spectrum, FLUORESCENCE, NITROGEN HETEROCYCLES, donor–acceptor systems, Chemistry, Second-harmonic generation, General Chemistry, Chromophore, 021001 nanoscience & nanotechnology, Fluorescence, 0104 chemical sciences, nonlinear optic, Physical chemistry, fluorescence, nitrogen heterocycles, Cyclic voltammetry, 0210 nano-technology
Abstract: A series of D-π-A chromophores based on [1,2,5]oxadiazolo[3,4-b]pyrazine electron-withdrawing group has been designed. The influence of the π-conjugated linker (1,4-phenylene and 2,5-thienylene) and the amino-electron-donating group (diphenylamino and carbazol-9-yl) was studied by cyclic voltammetry, UV-Vis and emission spectroscopy. The second order nonlinear optical properties were also studied using the electric field induced second harmonic generation (EFISH) method. The experimental results have been rationalized by theoretical DFT calculations. © 2020 Elsevier B.V. VEV is grateful to the financial support for the synthetic part from the Russian Foundation for Basic Research (Research Project No. 18-29-23045 mk).
Published: 2021
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29. 2,4-Distyryl- and 2,4,6-Tristyrylpyrimidines Synthesis and Photophysical Properties

Author: Oldřich Pytela, Filip Bureš, Françoise Robin-le Guen, Pascal Le Poul, Thierry Roisnel, Michaela Fecková, Milan Klikar, Sylvain Achelle, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Pardubice, Conseil Régional de Bretagne, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Substituent, Quantum yield, Chromophore, 010402 general chemistry, 01 natural sciences, Fluorescence, 0104 chemical sciences, chemistry.chemical_compound, Computational chemistry, Group (periodic table), Knoevenagel condensation, Density functional theory
Abstract: International audience; The synthesis of a series of 20 new 2,4,6-tristyrylpyrimidines and three new 2,4-distyrylpyrimidines by means of combination of Knoevenagel condensation and Suzuki-Miyaura cross-coupling reaction is reported. This methodology enables us to obtain chromophores with identical or different substituent on each arm. The photophysical properties of the compounds are described. Optical properties and time-dependent density functional theory calculations indicate that photophysical properties of target compounds are mainly affected by the nature of the electron-donating group in C4/C6 positions, except when the C2 substituent is a significantly stronger electron-donating group. However, the C2 substituent has a strong influence on emission quantum yield addition of a strong electron-donating group tends to decrease the fluorescence quantum yield, whereas a moderate electron-withdrawing group results in a significant increase of fluorescence quantum yield.
Published: 2018
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30. Incorporation of a ferrocene unit in the π-conjugated structure of donor-linker-acceptor (D-π-A) chromophores for nonlinear optics (NLO)

Author: Sylvain Achelle, Jean-Yves Saillard, Sébastien Gauthier, Alberto Barsella, Françoise Robin-le Guen, Raphaël J. Durand, Samia Kahlal, Maxime Ducamp, Nolwenn Cabon, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)
Subjects: Paper, Materials science, Nonlinear optics, General Chemical Engineering, Conjugated bridges, DFT calculation, Conjugated structures, Electrons, Conjugated system, Nonlinear optical properties, 010402 general chemistry, Iron compounds, 01 natural sciences, chemistry.chemical_compound, Synthesis, Moiety, Charge Transfer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Process Chemistry and Technology, Organic polymers, Electronwithdrawing, Organometallics, Optics, Chromophore, Chromophores, Intramolecular charge transfers, Acceptor, 0104 chemical sciences, Electrochemical behaviour, Crystallography, Ferrocene, chemistry, Electron-donating, Intramolecular force, Polar effect, Analogs
Abstract: In this paper we describe the synthesis, the electrochemical behaviour as well as the linear and nonlinear optical (NLO) properties of two push-pull derivatives bearing pyranylidene electron donating fragment, pyrimidine/methyl pyrimidinium electron withdrawing moiety and a ferrocene part in the π-conjugated bridge. The properties of these two compounds were compared to their analogues without ferrocene or pyranylidene fragments. Experimental results were completed with DFT calculations to gain further insight into the intramolecular charge transfer (ICT). All the results indicate a significant charge transfer through the ferrocene unit. The ICT is however more limited than in all organic analogues.
Published: 2018
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31. Triphenylamine-based allylidenemalononitrile chromophores synthesis, and photophysical and second-order nonlinear optical properties

Author: Zeynel Seferoğlu, Françoise Robin-le Guen, Alberto Barsella, Sylvain Achelle, Ergin Keleş, Nurgül Seferoğlu, Emine Çatal, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Scientific and Technological Research Council of Turkey (TUBITAK) [215Z567], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, 02 engineering and technology, General Chemistry, Chromophore, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, Branching (polymer chemistry), Triphenylamine, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Nonlinear optical, Aniline, Materials Chemistry, [CHIM]Chemical Sciences, Thermal stability, 0210 nano-technology
Abstract: International audience; A series of chromophores based on a mono-, di- or tri-substituted triphenylamine core and allylidenemalononitrile fragments has been designed. The linear and second order nonlinear optical properties as well as thermal stability of the chromophores have been studied experimentally. Structure-property relationships, in terms of the branching effect on the triphenylamine core and the influence of the aniline/coumarin part on the photophysical properties and NLO response, have been highlighted. The experimental results have been rationalized by theoretical calculations.
Published: 2018
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32. Photoluminescence Properties of Aryl-, Arylvinyl-, and Arylethynylpyrimidine Derivatives

Author: Julián Rodríguez-López, Sylvain Achelle, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Facultad de Ciencias y Tecnologias Quimicas, Universidad de Castilla-La Mancha (UCLM), ANII, Agencia Nacional de Investigación e Innovación, ERDF, European Regional Development Fund, AEI, Albert Ellis Institute, MINECO, Ministerio de Economía y Competitividad, CTQ2017-84561-P, FEDER, Federación Española de Enfermedades Raras, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM)
Subjects: Photoluminescence, Pyrimidine, 010405 organic chemistry, pyrimidines, Aryl, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence, 0104 chemical sciences, Push pull molecules, π-conjugated materials, chemistry.chemical_compound, chemistry, push-pull molecules, structure-property relationship, Molecule, [CHIM]Chemical Sciences, photoluminescence, quinazolines, Luminescence
Abstract: International audience; The extraordinary richness of push-pull molecules that incorporate pyrimidine rings as electron-withdrawing moieties in their structure is illustrated in this review. Interest in these π-extended systems has increased dramatically over the last two decades due to their fluorescence properties and potential applications in sensing and as luminescent materials. As many as 422 different molecules are presented in an effort to establish structure-property relationships, which are often difficult to elucidate. © 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim
Published: 2018
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33. Mono- and Diplatinum Polyynediyl Complexes as Potential Push–Pull Chromophores: Synthesis, Characterization, TD-DFT Modeling, and Photophysical and NLO Properties

Author: Alberto Barsella, Vincent Dorcet, Thierry Roisnel, Sébastien Gauthier, Françoise Robin-le Guen, Ariel Porter, Denis Jacquemin, Patricia Guevara Level, Sylvain Achelle, Nicolas Le Poul, RENARD, NICOLAS, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Center of Natural Sciences, Northern Kentucky University, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We deeply thank Prof. Bertrand Caro for his insightful advices and helpful comments. A.P. thanks the Northern Kentucky University (NKU) STEM International Research and Scholarly Exchange Program (IRSEP) for providing her internship and the NKU Center for Global Engagement and International Affairs for financial support. The theoretical calculations were carried out with the resources of the CCIPL in Nantes and of the IDRIS/CINES in Paris., Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Polyyne, Platinum complexes, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, NLO, 01 natural sciences, Inorganic Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, pyranylidene compounds, Chemistry, Ligand, Organic Chemistry, Second-harmonic generation, Chromophore, [CHIM.COOR] Chemical Sciences/Coordination chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Characterization (materials science), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Density functional theory, 0210 nano-technology, Platinum
Abstract: The syntheses, photophysical and electrochemical characterizations of four new mono- and diplatinum polyynediyl complex chromophores end-capped with diphenylpyranylidene and pentafluorophenyl moieties are described. The nonlinear optical properties (NLO) of these compounds have been investigated using the electric-field-induced second harmonic generation (EFISH) technique. While the inductive electron-withdrawing pentafluorophenyl ligand, the length of the polyyne linkers, and the number of platinum centers do not seem to significantly affect the NLO responses of these complexes, their structural configuration (V-shape vs linear shape) plays a significant role., La synthèse et les caractérisations photophysiques et électrochimiques de quatre chromophores mono - et diplatine polyynediyles porteurs de motifs diphenylpyranylidènes et pentafluorophényles sont décrits. Les propriétés d’optique non linéaire (NLO) de ces composés ont été étudiées par méthode EFISH. Les résultats montrent que la configuration structurale (forme en V vs. linéaire) du complexe affecte la réponse NLO, alors que la présence d’un ligand pentafluorométhyle, la longueur des espaceurs polyynes et le nombre de centres métalliques (Pt) semblent peu influents.
Published: 2018
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34. Ruthenium(II)-Catalyzed C–H (Hetero)Arylation of Alkenylic 1, n -Diazines ( n = 2, 3, and 4): Scope, Mechanism, and Application in Tandem Hydrogenations

Author: Thierry Roisnel, Sylvain Achelle, Françoise Robin-le Guen, Rafael Gramage-Doria, Christian Bruneau, Vincent Dorcet, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), CA15106, European Cooperation in Science and Technology, Centre National de la Recherche Scientifique, Université de Rennes 1, Rennes M?tropole, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: C-H acti- vation, Tandem, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, chemistry.chemical_element, Ruthenium catalyst, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Reductive elimination, 0104 chemical sciences, Catalysis, Ruthenium, chemistry, cross-coupling, Product formation, diazines, hydrogenation, ruthenium, Lone pair, Isomerization
Abstract: International audience; A general ruthenium(II)-catalyzed methodology enabling the (hetero)arylation of alkenylic C-H bonds utilizing a series of synthetically appealing diazines as directing groups is presented. Despite the presence of additional nitrogen lone pairs remote from the C-H bond activation site, which could eventually poison the catalyst, the reaction times are short (3 hours), thus being suitable for selective double C-H bond arylation. Mixtures of E:Z isomeric products were observed in some cases, which were further hydrogenated in a tandem manner in the presence of the remaining ruthenium catalyst from the first step; representing an alternative approach to more difficult C(sp 3)-H bond functionalization. According to mechanistic studies, the unexpected E:Z product formation seems to occur by thermal C=C bond isomerization after the reduc-tive elimination step.
Published: 2018
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35. Synthesis of Bromo- and Carboxylic Acid-Substituted Methylenepyrans

Author: Nikolay Vologdin, Sylvain Achelle, Sébastien Gauthier, Bertrand Caro, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Carboxylic acid, wittig reaction, Substituent, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, chemistry.chemical_compound, Organic chemistry, halogen-metal exchange, chemistry.chemical_classification, Bromine, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, electroactive compounds, aromatic bromide, 0104 chemical sciences, Methylenepyrans, chemistry, Wittig reaction, Electrophile, carboxylic acid, Absorption (chemistry), Cyclic voltametry
Abstract: International audience; In this contribution we describe a series of pyranylidene derivatives bearing bromine atoms in various positions. Some of these bromo derivatives have been converted in carboxylic acid by halogen-metal exchange reaction using gaseous CO2 as electrophile. Selected compounds have been studied by UV-visible absorption and cyclic voltametry to study the influence of the substituent on the pyranylidene core.
Published: 2014
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36. Synthesis and characterization of novel nitroxide organometallic Fischer-type carbene complexes

Author: Nolwenn Cabon, Françoise Robin-le Guen, Bertrand Caro, Pascal Le Poul, and Stéphane Golhen
Subjects: Nitroxide mediated radical polymerization, Hydrogen bond, Transition metal carbene complex, Organic Chemistry, Photochemistry, Biochemistry, Inorganic Chemistry, chemistry.chemical_compound, Aminolysis, Ferrocene, chemistry, Polymer chemistry, Materials Chemistry, Michael reaction, Molecule, Physical and Theoretical Chemistry, Carbene
Abstract: Reactions of 4-amino TEMPO with alkynylmethoxy Fischer type carbene complexes lead to unknown transition organometallic nitroxide spin labels. According to the temperature and the nature of the aromatic group of the initial alkynyl carbene, Michael adducts and aminolysis products were obtained in various proportions. The reaction was extended to ferrocenyl carbene complexes to obtain novel organometallic spin systems containing two kinds of redox units. Their constitution is in agreement with IR, elemental analysis and mass spectrometry. Single X-ray diffraction has confirmed the molecular structure of the complexes and has showed the existence of intra and intermolecular hydrogen bonds. These air-stable paramagnetic carbenes have interesting redox behaviours and paramagnetic properties.
Published: 2013
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37. Incorporation of a platinum center in the pi-conjugated core of push-pull chromophores for nonlinear optics (NLO)

Author: Sébastien Gauthier, Sylvain Achelle, Alberto Barsella, Jean-Yves Saillard, Samia Kahlal, Raphaël J. Durand, Françoise Robin-le Guen, Nicolas Le Poul, Laurianne Wojcik, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), R. D. thanks the French Ministry of Higher Education and Research for Ph. D. funding. The GENCI-CINES and GENCI-IDRISS French national computer centers are acknowledged for computational resources [grant x2016-087367], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diazine, 010405 organic chemistry, Stereochemistry, Intramolecular Charge Transfer, Pyranylidene, chemistry.chemical_element, Nonlinear optics, Chromophore, Conjugated system, 010402 general chemistry, 01 natural sciences, Redox, Acceptor, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, Platinum Complexes, chemistry, Intramolecular force, Nonlinear Optics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Platinum, ComputingMilieux_MISCELLANEOUS
Abstract: In this article, we describe the synthesis, redox characteristics, and linear and nonlinear optical (NLO) properties of seven new unsymmetrical push-pull diacetylide platinum-based complexes. These D-π-Pt-π-A complexes incorporate pyranylidene ligands as pro-aromatic donor groups (D), diazine rings as electron-withdrawing groups (A), and various aromatic fragments (styryl or thienylvinyl) as π-linkers separating the platinum diacetylide unit from the donor and the acceptor groups. This is one of the first examples of push-pull chromophores incorporating a platinum center in the π-conjugated core. The NLO properties of these complexes were compared with those of their purely organic analogues. All compounds (organic and organometallic) exhibited positive μβ values, which dramatically increased upon methylation of the pyrimidine fragment. However, this increase was even more significant in the complexes due to the presence of platinum in the π-conjugated core. The effects of the linker on the redox and spectroscopic properties of the complexes are also discussed. In addition, DFT calculations were performed in order to gain further insight into the intramolecular charge transfer (ICT) occurring through the platinum center.
Published: 2017
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38. Dipolar NLO Chromophores Bearing Diazine Rings as π-Conjugated Linkers

Author: Oldřich Pytela, Alberto Barsella, Milan Klikar, Kokou D. Dorkenoo, Sylvain Achelle, Françoise Robin-le Guen, Aleš Růžička, Filip Bureš, Pascal Le Poul, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institute of Organic Chemistry and Technology [University of Pardubice], University of Pardubice, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), M. K. and F. B. are indebted to the Ministry of Education, Youthand Sports of the Czech Republic (specific research)., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Diazine, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Conjugated system, Electron acceptor, Chromophore, 010402 general chemistry, Photochemistry, Triphenylamine, 01 natural sciences, 0104 chemical sciences, Pyridazine, chemistry.chemical_compound, chemistry, Polarizability, Intramolecular force
Abstract: International audience; The synthesis of a series of push-pull derivatives bearing triphenylamine electron-donating group, cyclopenta[c]thiophen-4,6-dione electron acceptor and various π-linkers including (hetero)aromatic fragments is reported. All target chromophores with systematically varied π-linker structure were further investigated by electrochemistry, absorption measurements, and EFISH experiments in conjunction with DFT calculations. Based on electrochemical and photophysical measurements, when a polarizable 2,5-thienylene moiety is embedded into the chromophore π-backbone the highest intramolecular charge transfer (ICT) is observed. Benzene, pyrimidine, and pyridazine derivatives exhibit lower polarizability and extent of the ICT across these π-linkers. The elongation of the π-conjugated system via additional ethenylene linker results in a significant reduction of the HOMO-LUMO gap and an enhancement of the NLO response. Whereas it does not significantly influence electrochemical and linear optical properties, the orientation of the pyrimidine ring seems to be a key parameter on the μβ value due to significant variation of the dipolar moment (μ) value. In 2a and 2c, pyrimidine is oriented to behave as an acceptor and thus generate dipolar molecule with μ above 5 D, whereas in 2b and 2d ground state dipole moment is significantly reduced. This study seems to indicate a high aromaticity of pyrimidine and pyridazine derivatives, close to the benzene analogues and significantly higher than thiophene analogues.
Published: 2017
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39. Emission properties of diazines chromophores: Structure-properties relationship

Author: Sylvain Achelle, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diazine, Design of experiment, 010405 organic chemistry, Diazines, General Chemical Engineering, Solvatochromism, General Physics and Astronomy, General Chemistry, Biphenylene, Chromophore, 010402 general chemistry, Ring (chemistry), Photochemistry, 01 natural sciences, 0104 chemical sciences, Photophysical properties, chemistry.chemical_compound, chemistry, Phenylene, Taguchi method, [CHIM]Chemical Sciences, Linker, Fluorosolvatochromism, Dichloromethane
Abstract: International audience; This article presents the photophysical properties of a series of diazine chromophores. The influence of five parameters has been studied: the presence of a diazine/benzodiazine fragment, the nature of the diazine fragment (1,3-diazine/1,4-diazine), the presence or not of an vinyl linker between diazine ring and phenylene fragments of the π-conjugated bridge, the presence of a phenylene/biphenylene linker and the nature of electron donating group (dimethylamino/diphenylamino). Taguchi's design of experiment combined with analysis of variance methodologies have been employed to highlight the main structural parameters influencing the position of absorption and emission maxima of dichloromethane solution and the extend of emission solvatochromic range exhibited by this family of chromophores. © 2017 Elsevier B.V.
Published: 2017
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40. Photophysical properties of acid-responsive triphenylamine derivatives bearing pyridine fragments: Towards white light emission

Author: Tomáš Mikýsek, David Miklík, Zdeňka Růžičková, Nolwenn Cabon, Oldřich Pytela, Jiří Tydlitát, Julián Rodríguez-López, Françoise Robin-le Guen, Sylvain Achelle, Filip Bureš, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), TE01020022, Technology Agency of the Czech Republic, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Photoluminescence, 010405 organic chemistry, Triphenylamine, Process Chemistry and Technology, General Chemical Engineering, Pyridine, White-light emission, Protonation, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Intramolecular force, OLED, [CHIM]Chemical Sciences, Polystyrene, Intramolecular charge transfer
Abstract: International audience; The synthesis, thermal, electrochemical, and optical properties of a series of triphenylamine derivatives bearing pyridine fragments and their trifluoroacetate salts are described. A dramatic increase in the intramolecular charge transfer is observed upon protonation, as evidenced by a significant reduction in the HOMO-LUMO gap and a red shift of both the absorption and the emission band. White photoluminescence was obtained in solution by the controlled protonation of blue emitting pyridine derivatives, which resulted in the yellow-orange emissive acidified form. In the solid state the emission color of doped polystyrene thin films could be tuned from steel blue to lawn green when the ratio of the protonated form was increased. These compounds have potential applications in the fabrication of multi-color OLEDs based on only one material. © 2017 Elsevier Ltd
Published: 2017
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41. New D-π-A-conjugated organic sensitizers based on α-pyranylidene donors for dye-sensitized solar cells

Author: Emilie Ferreira, Françoise Robin-le Guen, Nolwenn Cabon, Pascal Le Poul, Bertrand Caro, Yann Pellegrin, Fabrice Odobel, Aurélien Planchat, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), This work was supported by the University of Rennes 1, the CNRS, Lannion Tregor Commmunauté and Region Bretagne., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Absorption spectroscopy, Nanotechnology, Electron donor, Conjugated system, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, Biochemistry, law.invention, chemistry.chemical_compound, Magazine, law, Drug Discovery, Solar cell, α-Pyranylidene, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Electron acceptor, 0104 chemical sciences, Dye-sensitized solar cell, α-Thiopyranylidene, D-π-A molecules
Abstract: International audience; A series of new push-pull org. dyes incorporating a cyanoacrylic acid group as electron acceptor unit and α-chalcogenopyranylidene group (X = S; O) as electron donor unit has been synthesized, characterized and used as sensitizer for dye-sensitized solar cells (DSSCs). For the first time, α-pyranylidene and thiopyranylidene groups, have been evaluated in DSSC. To obtain the thermodn. values of the solar cell, an investigation of their electrochem. (CV) and optical properties (UV-vis absorption spectroscopy) is also reported.
Published: 2017
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42. Incorporation of pyrimidine fluorophores into poly(methylmethacrylate) polymer structures

Author: Françoise Robin-le Guen, Loïc Bodiou, Joël Charrier, Sylvain Achelle, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Fonctions Optiques pour les Technologies de l'informatiON (FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Université européenne de Bretagne - European University of Brittany (UEB)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Télécom Bretagne-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Université européenne de Bretagne - European University of Brittany (UEB)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Télécom Bretagne-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Chemistry(all), General Chemical Engineering, Halochromisme, Halochromism, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence, Polymerization, Solvatochromisme, Bathochromic shift, Polymer chemistry, Copolymer, [CHIM]Chemical Sciences, chemistry.chemical_classification, Polymérisation, 010405 organic chemistry, Solvatochromism, Transfert de charge intramoléculaire, General Chemistry, Polymer, Chromophore, 0104 chemical sciences, chemistry, Pyrimidine, Chemical Engineering(all), Intramolecular charge transfer, Macromolecule
Abstract: International audience; Three polymethyl methacrylate based copolymers bearing arylvinylpyrimidine chromophores have been synthesized in four steps. Spectral properties of the copolymers have been studied in solution, powder and thin films and compared with the corresponding free chromophores. The copolymers exhibit strong emission solvatochromism and act as polarity sensors. They also exhibit halochromism: when adding acid, a bathochromic shift is observed in absorption whereas a red-shifted fluorescence is observed with increased intensity for the methoxy-substituted macromolecule.; Trois copolymères à base de polyméthacrylate de méthyle portant des chromophores de type arylvinylpyrimidine ont été synthétisés en quatre étapes. Les propriétés spectrales des copolymères ont été étudiées en solution, sous forme de film et de poudre et comparées au chromophore libre correspondant. Les copolymères présentent un fort solvatochromisme d’émission et sont donc susceptibles d’être utilisés comme sonde de polarité. Ils présentent également des propriétés d’halochromisme: en milieu acide, un déplacement bathochrome du spectre d’absorption peut être observé. Dans le cas du copolymère substitué par un groupement méthoxy, un déplacement vers le rouge de la bande d’émission est également observé.
Published: 2016
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43. Luminescence Behavior of Protonated Methoxy-Substituted Diazine Derivatives: Towards White Light Emission

Author: Claudine Katan, Sylvain Achelle, Julián Rodríguez-López, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Facultad de Ciencias y Tecnologias Quimicas, Universidad de Castilla-La Mancha (UCLM), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM)
Subjects: Diazine, Quenching (fluorescence), Pyrazine, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Protonation, 010402 general chemistry, Photochemistry, 01 natural sciences, Acceptor, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, General Energy, Quinoxaline, chemistry, Molecule, Physical and Theoretical Chemistry, Luminescence
Abstract: acknowledge the HPC resources of CINES and of IDRIS under the allocations 2016-[x2016080649] made by GENCI (Grand Equipment National de Calcul Intensif); International audience; White light emitting diodes (WOLEDs) are an efficient alternative to conventional lighting sources. Nevertheless, approaches to obtain WOLEDs still require complex processes that lead to high costs. In this sense, the use of a single emitting material that can take two forms of complementary emitting colors has emerged as a new strategy for the fabrication of WOLEDs. In this paper we describe the luminescent behavior upon protonation of a series of D-π-A push-pull molecules based on a methoxyphenyl or methoxynaphthyl donor unit and a diazine acceptor unit with different π-bridges. The effect of protonation on the emission properties depends on the nature of the diazine ring. The addition of trifluoroacetic acid (TFA) to pyrazine and quinoxaline derivatives led to quenching of the fluorescence whereas pyrimidine derivatives remained luminescent after protonation, which prompted a color change in the emission due to the appearance of a new red-shifted band in the spectra. These results were rationalized with the help of TD-TFT calculations. White photoluminescence could be obtained in solution by the controlled protonation of some pyrimidines, which resulted in the formation of an orange emissive acidified form. This phenomenon opens up the possibility of exploiting these materials for the fabrication of WOLEDs.
Published: 2016
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44. Tripodal molecules with triphenylamine core, diazine peripheral groups and extended π-conjugated linkers

Author: Daniel Cvejn, Arnaud Spangenberg, Nolwenn Cabon, Oldřich Pytela, Filip Bureš, Françoise Robin-le Guen, Jean-Pierre Malval, Sylvain Achelle, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institute of Organic Chemistry and Technology [University of Pardubice], University of Pardubice, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), D. C., O. P. and F. B. are indebted to the Czech Science Foundation (13-01061S). N. C. gratefully acknowledges Dr. F. Gloaguen and UMR CNRS 6521 for their support., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diazine, 010405 organic chemistry, Diazines, Process Chemistry and Technology, General Chemical Engineering, Solvatochromism, Sonogashira coupling, [CHIM.MATE]Chemical Sciences/Material chemistry, Chromophore, Conjugated system, 010402 general chemistry, Triphenylamine, Photochemistry, Triphenylamines, 01 natural sciences, Fluorescence, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, chemistry, Intramolecular force, Molecule, [CHIM]Chemical Sciences, Nonlinear Optics, Intramolecular charge transfer
Abstract: International audience; A series of five octupolar molecules with central triphenylamine donor and peripheral diazine electron-withdrawing groups has been prepared. These structures possess extended π-spacer comprising multiple bonds in a combination with 1,4-phenylene and 2,5-thienylene subunits. Starting from tris(4-ethynylphenyl)amine, the key step in the preparation of the chromophores involves triple Sonogashira cross-coupling reaction. The photophysical properties of the compounds are described. A strong positive emission solvatochromism, typical for dyes featuring Intramolecular Charge Transfer (ICT), is observed, two-photon absorption (2PA) properties were also measured. Linear and nonlinear optical properties as well as electronic properties measured by cyclic voltametry and supported by DFT calculation were used to elucidate structure-property relationships
Published: 2016
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45. The synthesis of flexible tetrapyridylethanes from pyridylpyrylium dications

Author: Bertrand Caro, Stéphane Golhen, Françoise Robin-le Guen, Nicolas Le Poul, Pascal Le Poul, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)
Subjects: chemistry.chemical_classification, 010405 organic chemistry, General Chemistry, Crystal structure, 010402 general chemistry, Electrochemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, Pyridine ligand, 0104 chemical sciences, Coordination complex, Aminolysis, chemistry, Materials Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Oxidation process
Abstract: International audience; New tetrapyridylethanes can be prepd. as new tetradentate pyridine ligands via the aminolysis reaction of pyrylium dications, using an original oxidn. process of phenylpyridyl methylenepyrans. Crystal structure anal., and spectroscopic and electrochem. studies show the possibility for using these new ligands in coordination chem.
Published: 2016
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46. Proaromatic pyranylidene chalcogen analogues and cyclopenta[c]thiophen-4,6-dione as electron donors and acceptor in efficient charge-transfer chromophores

Author: Sylvain Achelle, Françoise Robin-le Guen, Alberta Barsella, Parmeshwar Bapurao Solanke, Nolwenn Cabon, Bertrand Caro, Filip Bureš, Jan Podlesný, Milan Klikar, Oldřich Pytela, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), 638857, ERC, European Research Council, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chalcogenopyranylidene, General Chemical Engineering, Fundamental properties, 010402 general chemistry, Photochemistry, 01 natural sciences, push-pull, chemistry.chemical_compound, Chalcogen, Charge transfer, Thiophene, Moiety, Molecule, Chalcogenopyranylidene, [CHIM]Chemical Sciences, Push pull, chemistry.chemical_classification, 010405 organic chemistry, Process Chemistry and Technology, Electronwithdrawing, charge transfer, Chromophore, Electron acceptor, Push-pull chromophores, Chromophores, Acceptor, Structural variations, 0104 chemical sciences, polymethines, non linear optics, Polymethines, chemistry, Pyran, Electron acceptor moieties
Abstract: International audience; Fifteen new push-pull chromophores based on a proaromatic pyranylidene donor and its chalcogen analogues and various electron acceptor moieties were synthesized in a straightforward manner. These model molecules were designed and prepared to investigate the concept of proaromaticity as a tool to tune the fundamental properties of push-pull systems. All target chromophores with systematically varied structure were further investigated by electrochemistry, absorption spectra, and EFISH experiment in conjunction with DFT calculations. Employing structural variations such as chalcogen/acceptor replacement, extension of the π-system, and the position of substitution along the pyran ring, the HOMO-LUMO gap can be tuned within the range of 2.18 to 1.41 eV. A new and powerful electron withdrawing moiety, combining features of polarizable thiophene and successful indane-1,3-dione acceptor, cyclopenta[c]thiophen-4,6-dione (ThDione) has also been developed. © 2016 Elsevier Ltd
Published: 2016
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47. Dipicolylamine styryldiazine derivatives: Synthesis and photophysical studies

Author: Filip Bureš, Julián Rodríguez-López, Françoise Robin-le Guen, Sylvain Achelle, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Facultad de Ciencias y Tecnologías Químicas de Ciudad Real (UCLM), Institute of Organic Chemistry and Technology [University of Pardubice], University of Pardubice, We thank Jérôme Orain and Kevin Babe for some preliminary syntheses. J.R.-L. thanks the Junta de Comunidades de Castilla-La Mancha/FEDER (EU) – project PEII-2014-005-A – for financial support., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diazine, Chemistry, Diazines, Process Chemistry and Technology, General Chemical Engineering, Metal cations, Protonation, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Photochemistry, Acceptor, Fluorescence, chemistry.chemical_compound, Dipicolylamine, Intramolecular force, Molecule, π-conjugated systems, [CHIM]Chemical Sciences, Aldol condensation, Intramolecular charge transfer, Push–pull molecules
Abstract: Different D–π–A push–pull molecules in which dipicolylamine (DPA) is used as the donor group, different diazines as the acceptor groups, and styryl as the π-conjugated spacer have been synthesized in a straightforward manner by aldol condensation of 4-(di-2-picolylamino)benzaldehyde and the appropriate methyldiazine. All of the compounds showed π–π* transitions in the UV or visible region and the emission of yellow-green light upon irradiation. Significant red shifts were observed in the fluorescence emission maxima of these compounds on increasing the solvent polarity, a finding that suggests the formation of an intramolecular charge-separated emitting state that is also supported by semi-empirical calculations. In some cases, protonation led to marked color changes, thus showing the ability of these molecules to function as colorimetric pH sensors. The DPA and diazine units can act as coordination sites for metal cations such as Zn 2+ , Cd 2+ or Hg 2+ , leading to a blue or red shift in the fluorescence spectra due to the change in the intramolecular charge transfer properties. This phenomenon could become a powerful tool for the creation of multiple emission colors with a single molecule after suitable design.
Published: 2015
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48. Convenient synthesis of dithiafulvene carbene complexes as potential precursors of extended TTF

Author: B. Caro, Françoise Robin-le Guen, and Pascal Le Poul
Subjects: Allylic rearrangement, chemistry.chemical_compound, chemistry, Transition metal carbene complex, Organic Chemistry, Drug Discovery, Condensation, Polymer chemistry, Organic chemistry, Biochemistry, Carbene, Carbanion
Abstract: The condensation of α-carbanion of Fischer-type carbene complex with 2-thiomethyl-1,3-dithiolium salts 1 gave new heterocyclic organometallic carbenes 2 potentially precursors of extended TTF. Reaction of allylic carbanion 4 derived from (methoxypropenyl)pentacarbonyl carbene complex afforded a mixture of monoheterocyclic condensation products 7 and diheterocyclic carbene complexes 8 produced from successive α and γ attacks of the heterocyclic cations.
Published: 2004
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49. Improvement of the quadratic non-linear optical properties of pyrimidine chromophores by N-methylation and tungsten pentacarbonyl complexation

Author: Xiaoyang Che, Filip Bureš, Jean-Yves Saillard, Julien Vallet, Alberto Barsella, Sylvain Achelle, Bertrand Caro, Samia Kahlal, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Technology, University of Pardubice, Faculty of Chemical Technology, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institute of Organic Chemistry and Technology [University of Pardubice], University of Pardubice, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Pyrimidine, Chemistry, Process Chemistry and Technology, General Chemical Engineering, chemistry.chemical_element, Second-harmonic generation, Nonlinear optics, N methylation, Chromophore, Tungsten, Ring (chemistry), Photochemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Nonlinear system, chemistry.chemical_compound, Computational chemistry
Abstract: International audience; In this contribution, we report the synthesis of two series of compds.: 4-(arylvinyl)-1-methylpyrimidinium derivs. and tungsten pentacarbonyl complexes of 4-(arylvinyl)pyrimidines. Their second order non-linear properties, measured by Elec.-Field Induced Second Harmonic generation (EFISH) method, and their photophys. behavior were thoroughly investigated and compared to the corresponding 4-(arylvinyl)pyrimidines. A strong enhancement of the NLO response was obsd. upon methylation or complexation by W(CO)5 of the pyrimidine ring. DFT theor. calcns. were performed to provide complementary insights on the structure-properties relationships in particular concerning the amplitude of the NLO response.
Published: 2015
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50. Protonable pyrimidine derivative for white light emission

Author: Sylvain Achelle, Nolwenn Cabon, Julián Rodríguez-López, Françoise Robin-le Guen, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Facultad de Ciencias y Tecnologías Químicas de Ciudad Real (UCLM), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_compound, Photoluminescence, Pyrimidine, Chemistry, General Chemical Engineering, education, OLED, White light, Blue emitting, [CHIM]Chemical Sciences, Protonation, General Chemistry, Photochemistry
Abstract: International audience; White photoluminescence both in soln. and the solid-state was obtained by the controlled protonation of a blue emitting 4,6-bis(arylvinyl)pyrimidine, which resulted in the formation of an orange emissive acidified form. This dye has potential applications in the fabrication of white OLEDs based on only one material.
Published: 2015
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