79 results on '"Daniel Escudero"'
Search Results
2. Does Twisted π-Conjugation Framework Always Induce Efficient Intersystem Crossing? A Case Study with Benzo[b]- and [a]Phenanthrene-Fused BODIPY Derivatives and Identification of a Dark State
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Daniel Escudero, Antonio Barbon, Qinglin Guan, Jianzhang Zhao, Andrei A. Sukhanov, Gagik G. Gurzadyan, Denis Jacquemin, Yuxin Yan, Violeta K. Voronkova, Yongheng Xing, and Manon H. E. Bousquet
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Materials science ,PARAMAGNETIC-RESONANCE ,MOLECULAR DESIGN ,intersystem crossing ,TRIPLET EXCITED-STATE ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Spectral line ,law.invention ,chemistry.chemical_compound ,law ,0103 physical sciences ,Materials Chemistry ,Singlet state ,Physical and Theoretical Chemistry ,Triplet state ,Electron paramagnetic resonance ,PHOTOINDUCED ELECTRON-TRANSFER ,Science & Technology ,SINGLET OXYGEN ,010304 chemical physics ,Chemistry, Physical ,Fluorescence ,0104 chemical sciences ,Surfaces, Coatings and Films ,Chemistry ,Dark state ,Intersystem crossing ,PHOTON UP-CONVERSION ,chemistry ,LOW-POWER ,PHOTOPHYSICAL PROPERTIES ,Physical Sciences ,METAL-COMPLEXES ,BODIPY ,CHARGE SEPARATION - Abstract
The photophysical properties, especially the intersystem crossing (ISC) of two heavy-atom-free BODIPY derivatives with twisted π-conjugated frameworks (benzo[b]-fused BODIPY, BDP-B; and [a]phenanthrene-fused BODIPY, BDP-P), are studied with steady-state and time-resolved optical and electron paramagnetic resonance (TREPR) spectroscopic methods as well as with ADC(2) theoretical investigations. Interestingly, BDP-B has a planar π-conjugation framework, but it displays weaker UV-vis absorption (ε = 3.8 × 104 M-1 cm-1 at 569 nm) and fluorescence (ΦF < 0.1%), a short-lived singlet-excited state (fluorescence lifetime, τF = 0.2 ns), and a long-lived triplet state (τT = 132.3 μs). In comparison, the more twisted BDP-P shows stronger UV-vis absorption (ε = 9.8 × 104 M-1 cm-1 at 640 nm) and fluorescence (ΦF = 70%), longer singlet-excited-state lifetime (τF = 6.4 ns), and shorter triplet-state lifetime (τT = 18.9 μs). In contrast to helicenes (ΦT = ca. 90%), the ISC of BDP-P and BDP-B is nonefficient (ΦT < 23%). The electron spin selectivity of the ISC of the derivatives is different, manifested by the phase pattern of the TREPR spectra as AAEAEE and EEEAAA for BDP-B and BDP-P, respectively. The spatially confined T1 state wave function of the twisted molecule keeps the T1 state energy high (1.44-1.61 eV). A dark S1 state was identified for BDP-B. This work demonstrated that the twisted π-conjugated framework does not necessarily induce efficient ISC and we found a dark singlet state for BODIPY, which is rare. ispartof: JOURNAL OF PHYSICAL CHEMISTRY B vol:125 issue:23 pages:6280-6295 ispartof: location:United States status: published
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- 2021
3. Ligand-Controlled Selectivity in the Pd-Catalyzed C–H/C–H Cross-Coupling of Indoles with Molecular Oxygen
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Prashant Kumar, Dirk De Vos, Daniel Escudero, Igor Beckers, and Besir Krasniqi
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chemistry.chemical_element ,Homogeneous catalysis ,010402 general chemistry ,01 natural sciences ,Oxygen ,Catalysis ,C-H activation ,Indole test ,Science & Technology ,Chemistry, Physical ,010405 organic chemistry ,Ligand ,General Chemistry ,palladium ,homogeneous catalysis ,Combinatorial chemistry ,3. Good health ,0104 chemical sciences ,Coupling (electronics) ,Chemistry ,indole ,chemistry ,Physical Sciences ,C-C coupling ,Selectivity ,oxygen ,Palladium - Abstract
Two indoles linked by a C–C bond have recently emerged as promising scaffolds in medicinal chemistry. Their synthesis, however, involves a multitude of reaction steps. So far, the direct C–H/C–H cr...
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- 2021
4. Formation of Excimers in Isoquinolinyl Pyrazolate Pt(II) Complexes: Role of Cooperativity Effects
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Prashant Kumar, Nawee Kungwan, Yun Chi, Daniel Escudero, and Chattarika Sukpattanacharoen
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chemistry.chemical_classification ,Steric effects ,010405 organic chemistry ,Chemistry ,Dimer ,Trimer ,Cooperativity ,Interaction energy ,010402 general chemistry ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Excited state ,Non-covalent interactions ,Density functional theory ,Physical and Theoretical Chemistry - Abstract
The interplay between noncovalent interactions involving metal complexes may lead to the formation of aggregates (i.e., ground state dimers, trimers, n-mers, etc.), and this is often linked to dramatic changes in their physical and chemical properties as compared to the original properties of the isolated units. Dimers and trimers can also be formed in the excited state potential energy surfaces, i.e., excimers. Excimers are short-lived but are also often characterized by different optical properties from those of the isolated units. Understanding the nature of noncovalent interactions and the presence or not of cooperativity effects in both aggregates and excimers is thus extremely important to rationalize these variations. In this study, we present computational investigations on isoquinolinyl pyrazolate Pt(II) complexes. Our results highlight that cooperativity effects between noncovalent interactions, which are modulated by sterically demanding substituents and metallophilic Pt···Pt interactions, are present only on certain investigated excimers. We use density functional theory (DFT) calculations to examine the cooperativity effects and the changes in the photophysical properties. Different descriptors of cooperativity effects between noncovalent interactions, including the synergetic, genuine nonadditive, and total interaction energies, were evaluated for a series of Pt(II) aggregates and excimers. In addition, energy decomposition analysis (EDA) calculations were performed to rationalize the origins of the cooperative effects. The cooperative effects in trimer excimers (in their lowest triplet excited state, i.e., T1) led to shortened Pt···Pt contacts as compared to the trimer aggregates. Furthermore, this synergy between noncovalent interactions is ultimately responsible for the formation of the excimers and the striking changes in the measured photophysical properties. More in detail, we report a change in the character of the lowest-lying triplet excited state when going from dimer excimers (i.e., of mixed triplet ligand-centered and triplet metal-to-ligand charge transfer (3LC/3MLCT) character) to trimer excimers (i.e., of triplet metal-metal-to-ligand charge transfer (3MMLCT) character). The EDA reveals that the total interaction energy on trimer excimers is subtly controlled by the electrostatic and dispersion terms. ispartof: INORGANIC CHEMISTRY vol:59 issue:24 pages:18253-18263 ispartof: location:United States status: published
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- 2020
5. Unusual spectroscopic and photophysical properties of solvatochromic BODIPY analogues of Prodan
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Daniel Escudero, Noёl Boens, Erhong Hao, Angel Orte, Lijuan Jiao, Fan Lv, Maria J. Ruedas-Rama, Eva M. Talavera-Rodriguez, Juan A. González-Vera, and Xing Guo
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DYNAMICS ,Technology ,Engineering, Chemical ,General Chemical Engineering ,Materials Science ,BETA ,Photochemistry ,PARAMETERS ,PROBES ,chemistry.chemical_compound ,Engineering ,FLUORESCENCE-SPECTRA ,ABSORPTION ,Molecule ,Materials Science, Textiles ,SOLVENT ,Science & Technology ,Chemistry ,Process Chemistry and Technology ,Solvatochromism ,Rational design ,Quantum Chemistry ,Fluorescence ,Acceptor ,Chemistry, Applied ,Donor group ,Excited State ,Photophysics ,Physical Sciences ,Solvent effects ,BODIPY ,DYES ,Boron Dipyrromethene ,POLARITY ,ENVIRONMENTS - Abstract
Here, we report the synthesis of two isomeric BODIPY-based fluorescent molecules with a diethylamino donor group and an acetyl acceptor group at positions 5 and 2 (or 3), respectively, on the boron dipyrromethene core. The structure of the new BODIPY dyes is similar to Prodan, probably the most widely used solvatochromic probe, but with the donor and acceptor groups attached to an electron-poor heteroaromatic core. Interestingly, these BODIPY dyes exhibit unusual spectroscopic and photophysical properties, involving inverse solvatochromic behavior. An in-depth study of the solvent effects and quantum-chemical calculations have been performed to assess the basis for such spectroscopic properties and the effect of the position of the substitution. This work points towards a rational design of new fluorescent probes, based on understanding their spectroscopic and photophysical behavior.
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- 2022
6. High-Valent Pyrazolate-Bridged Platinum Complexes: A Joint Experimental and Theoretical Study
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Lorenzo Arnal, Daniel Escudero, Sara Fuertes, Antonio Martin, Violeta Sicilia, Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Ministerio de Economía y Competitividad (España), Gobierno de Aragón, European Commission, KU Leuven, and Research Foundation - Flanders
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ORGANIC MONOCHLORO DERIVATIVES ,CYCLOPLATINATED COMPLEXES ,MECHANISM ,Science & Technology ,IRIDIUM DIMERS ,H BOND ACTIVATION ,RHODIUM ,Inorganic Chemistry ,ORGANOMETALLIC CHEMISTRY ,Chemistry ,DINUCLEAR COMPLEXES ,METHYL-IODIDE ,Physical Sciences ,Chemistry, Inorganic & Nuclear ,OXIDATIVE-ADDITION ,Physical and Theoretical Chemistry - Abstract
Complexes [{Pt(C^C*)(μ-pz)}2] (HC^C*A = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene 1a, HC^C*B = 1-phenyl-3-methyl-1H-imidazol-2-ylidene 1b) react with methyl iodide (MeI) at room temperature in the dark to give compounds [{PtIV(C^C*)Me(μ-pz)}2(μ-I)]I (C^C*A2a, C^C*B2b). The reaction of 1a with benzyl bromide (BnBr) in the same conditions afforded [Br(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)Bn] (5a), which by heating in BnBr(l) became [{PtIV(C^C*A)Bn(μ-pz)}2(μ-Br)]Br (6a). Experimental investigations and density functional theory (DFT) calculations on the mechanisms of these reactions from 1a revealed that they follow a SN2 pathway in the two steps of the double oxidative addition (OA). Based on the DFT investigations, species such as [(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)R]X (RX = MeI Int-Me, BnBr Int-Bn) and [(C^C*A)PtII(μ-pz)2PtIV(C^C*A)(R)X] (RX = MeI Int′-Me, BnBr Int′-Bn) were proposed as intermediates for the first and the second OA reactions, respectively. In order to put the mechanisms on firmer grounds, Int-Me was prepared as [(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)Me]BF4 (3a′) and used to get [I(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)Me](4a), [(C^C*A)PtII(μ-pz)2PtIV(C^C*A)(Me)I](Int′-Me), and [{PtIV(C^C*)Me(μ-pz)}2(μ-I)]BF4 (2a′). The single-crystal X-ray structures of 2a, 2b, 3a′, and 5a along with the mono- and bi-dimensional 1H and 195Pt{1H} NMR spectra of all the named species allowed us to compare structural and spectroscopic data for high-valent complexes with the same core [{Pt(C^C*)(μ-pz)}2] but different oxidation states., This work was supported by the Spanish Ministerio de Economia y Competitividad (Ministerio de Ciencia Innovacion y Universidades)/FEDER (Project PGC2018-094749-B-I00), by the Gobierno de Aragon (Grupo E17_20R: Química Inorgánica y de los Compuestos Organometálicos) and by Internal Funds KU Leuven and FWO. L.A. acknowledges the support of a grant from the Gobierno de Aragón.
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- 2022
7. Heteropolymetallic architectures as snapshots of transmetallation processes at different degrees of transfer
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David Campillo, Daniel Escudero, Miguel Baya, Antonio Martín, Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Gobierno de Aragón, KU Leuven, and Netherlands Organization for Scientific Research
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Science & Technology ,CATALYSIS ,Chemistry, Multidisciplinary ,fluxionality ,Organic Chemistry ,General Chemistry ,DFT calculations ,STEP ,COUPLINGS ,Catalysis ,Chemistry ,Physical Sciences ,PD ,metal-metal bond ,COMPLEXES ,cooperative catalysis ,METALS ,transmetallation ,TRANSITION - Abstract
Novel heteropolymetallic architectures have been built by integrating Pd, Au and Ag systems. The dinuclear [(CNC)(PPh3)Pd-G11M(PPh3)](ClO4) (G11M=Au (3), Ag (4); CNC=2,6-diphenylpyridinate) and trinuclear [{(CNC)(PPh3)Pd}2G11M](ClO4) (G11M=Au (6), Ag (5)) complexes have been accessed or isolated. Structural and DFT characterization unveil striking interactions of one of the aryl groups of the CNC ligand(s) with the G11M center, suggesting these complexes constitute models of transmetallation processes. Further analyses allow to qualitatively order the degree of transfer, proving that Au promotes the highest one and also that Pd systems favor higher degrees than Pt. Consistently, Energy Decomposition Analysis calculations show that the interaction energies follow the order Pd−Au > Pt−Au > Pd−Ag > Pt−Ag. All these results offer potentially useful ideas for the design of bimetallic catalytic systems., This work was supported by the Spanish MICIU/FEDER (Project PGC2018-094749-B−I00) and the Gobierno de Aragón (Grupo E17_20R). BIFI (Instituto de Biocomputación y Física de Sistemas Complejos) and CESGA (Centro de Supercomputación de Galicia) are acknowledged for allocation of computational resources.. D.C. also thanks the Gobierno de Aragón for a grant. D.E. acknowledges KU Leuven Internal Funds and FWO.
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- 2022
8. Heteroatom substitution effect on electronic structures, photophysical properties, and excited-state intramolecular proton transfer processes of 3-hydroxyflavone and its analogues: A TD-DFT study
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Rusrina Salaeh, Daniel Escudero, Nawee Kungwan, Vinich Promarak, and Chattarika Sukpattanacharoen
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Excited state intramolecular proton transfer (ESIPT) ,FLUORESCENT-PROBE ,Heteroatom ,3-Hydroxyflavone derivatives ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Analytical Chemistry ,Inorganic Chemistry ,chemistry.chemical_compound ,CHARGE-TRANSFER ,Molecular orbital ,Heteroatom effect ,MODULATION ,Spectroscopy ,Science & Technology ,Chemistry, Physical ,DENSITY-FUNCTIONAL THERMOCHEMISTRY ,RANGE ,DERIVATIVES ,010405 organic chemistry ,Hydrogen bond ,Organic Chemistry ,3-Hydroxyflavone ,Conical intersection ,TRANSFER ESIPT ,0104 chemical sciences ,Chemistry ,chemistry ,2-(2'-HYDROXYPHENYL)BENZOXAZOLE ,Intramolecular force ,Physical Sciences ,Density functional theory ,TD-DFT ,H-BOND ,EMISSION ,Ground state - Abstract
The effects of the electron-donating capacity altered by heteroatom substituents on the electronic structures, photophysical properties, and excited-state intramolecular proton transfer (ESIPT) processes of 3HX analogues (3HF, 3HQ, 3HTF, and 3HSO where X = O, NH, S, and SO2, respectively) have been investigated by both static calculations and dynamic simulations using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods at B3LYP/TZVP level for ground state (S0) and excited-state (S1), respectively. The static results indicate that the intramolecular hydrogen bonds of all molecules are strengthened in the S1 state, confirmed by the red-shift of IR vibrational spectra and the topology analysis. Heteroatom substitutions cause the red-shift on enol absorption and keto emission spectra of 3HX with relatively larger Stoke shift corresponding to their HOMO−LUMO gaps compared with that of 3HF. Frontier molecular orbitals (MOs) show that upon the photoexcitation, the charge redistribution between the proton donor and proton acceptor groups have induced the ESIPT process. Moreover, the potential energy curves (PECs) of proton transfer (PT) processes of all molecules reveal that the PT processes of all molecules are most likely to proceed in the S1 state because of low barrier and exothermic reaction. The chance of ESIPT for all molecules is in this order: 3HSO > 3HTF > 3HF > 3HQ. The results of dynamic simulations confirm that the ESIPT processes of all molecules easily occur with the ultrafast time scale (48, 55, 60, 70 fs for 3HSO, 3HTF, 3HF, and 3HQ, respectively). Furthermore, the PT time is anti-correlated with the electronegativity of heteroatoms in 3HX, supported by Mulliken analysis. The ESIPT process of 3HSO is the fastest among 3HX in accordance with its highest intramolecular hydrogen bond strength, lowest PT barrier, and highest exothermic reaction. Nevertheless, after the ESIPT is complete, the twisted structure of 3HSO has initiated the conical intersection, leading to no keto emission observed in the experiment.
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- 2019
9. Computational Protocol to Calculate the Phosphorescence Energy of Pt(II) Complexes: Is the Lowest Triplet Excited State Always Involved in Emission? A Comprehensive Benchmark Study
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Daniel Escudero and Prashant Kumar
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Inorganic Chemistry ,Coupled cluster ,Chemistry ,Excited state ,Density functional theory ,Phosphor ,Physical and Theoretical Chemistry ,Triplet state ,Relativistic quantum chemistry ,Phosphorescence ,Molecular physics ,Excitation - Abstract
The reliable calculation of phosphorescence energies of phosphor materials is at the core of designing efficient phosphorescent organic light-emitting diodes (PhOLEDs). Therefore, it is of paramount importance to have a robust computational protocol to perform those calculations in a black-box manner. In this work, we use Domain-Based Local Pair Natural Orbital Coupled Cluster theory with single, double, and perturbative triple excitation (DLPNO-CCSD(T)) calculations to attain the phosphorescence energies of a large pool of Pt(II) complexes. Several approaches to incorporate relativistic effects in our calculations were tested. In addition, we have used the DLPNO-CCSD(T) values (i.e., our best theoretical values) to assess the performance of different flavors of density functional theory including pure, hybrid, meta-hybrid, and range-separated functionals. Among the tested functionals, the M06HF functional provides the best values compared with the DLPNO-CCSD(T) ones, with a mean absolute deviation (MAD) value of 0.14 eV. In its turn, and thanks to the increased accuracy achieved in the calculation of phosphorescence energies, we also demonstrate that not all of the investigated complexes emit from their lowest-lying triplet state (T1). The outlier complexes include different complex photophysical scenarios and both Kasha and anti-Kasha types of complexes. Finally, we provide a general computational protocol to pre-screen whether T1 is actually the emissive state and to accurately calculate the phosphorescence energies of Pt(II) complexes. ispartof: INORGANIC CHEMISTRY vol:60 issue:22 pages:17230-17240 ispartof: location:United States status: published
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- 2021
10. Chameleonic Photo- and Mechanoluminescence in Pyrazolate-Bridged NHC Cyclometalated Platinum Complexes
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Antonio Martín, Daniel Escudero, Sara Fuertes, Lorenzo Arnal, Violeta Sicilia, KU Leuven, Ministerio de Economía y Competitividad (España), Ministerio de Ciencia, Innovación y Universidades (España), Gobierno de Aragón, Agencia Estatal de Investigación (España), and European Commission
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Mechanochromic luminescence ,TRIPLET EXCITED-STATE ,EFFICIENT ,chemistry.chemical_element ,MECHANOCHROMIC LUMINESCENCE ,Inorganic Chemistry ,DINUCLEAR PLATINUM(II) ,PT(II) COMPLEXES ,Chemistry, Inorganic & Nuclear ,Molecule ,Physical and Theoretical Chemistry ,Conformational isomerism ,Science & Technology ,Chemistry ,CENTER-DOT-PT ,Crystallography ,EMITTERS ,PHOTOPHYSICAL PROPERTIES ,Intramolecular force ,Excited state ,Physical Sciences ,BINUCLEAR COMPLEXES ,EMISSION ,Platinum ,Excitation ,Mechanoluminescence - Abstract
DFT investigations on the ground (GS) and the first triplet (T1) excited state potential energy surfaces (PES) were performed on a new series of platinum-butterfly complexes, [{Pt(C∧C*)(μ-Rpz)}2] (Rpz: pz, 1; 4-Mepz, 2; 3,5-dmpz, 3; 3,5-dppz, 4), containing a cyclometalated NHC in their wings. The geometries of two close-lying local minima corresponding to butterfly spread conformers, 1s–4s, and butterfly folded ones, 1f–4f, with long and short Pt–Pt separations, respectively, were optimized in the GS and T1 PES. A comparison of the GS and T1 energy profiles revealed that an opposite trend is obtained in the relative stability of folded and spread conformers, the latter being more stabilized in their GS. Small ΔG (s/f) along with small-energy barriers in the GS support the coexistence of both kinds of conformers, which influence the photo- and mechanoluminescence of these complexes. In 5 wt % doped PMMA films in the air, these complexes exhibit intense sky-blue emissions (PLQY: 72.0–85.9%) upon excitation at λ ≤ 380 nm arising from 3IL/MLCT excited states, corresponding to the predominant 1s–4s conformers. Upon excitation at longer wavelengths (up to 450 nm), the minor 1f–4f conformers afford a blue emission as well, with PLQY still significant (40%–60%). In the solid state, the as-prepared powder of 4 exhibits a greenish-blue emission with QY ∼ 29%, mainly due to 3IL/3MLCT excited states of butterfly spread molecules, 4s. Mechanical grinding resulted in an enhanced and yellowish-green emission (QY ∼ 51%) due to the 3MMLCT excited states of butterfly folded molecules, 4f, in such a way that the mechanoluminescence has been associated with an intramolecular structural change induced by mechanical grinding., This work was supported by the Spanish Ministerio de Economia y Competitividad (Ministerio de Ciencia Innovacion y Universidades)/FEDER (Project PGC2018–094749–B-I00), by the Gobierno de Aragon (Grupo E17_20R: Quimica Inorganica y de los Compuestos Organometallicos), and by Internal Funds KU Leuven.
- Published
- 2021
11. A macrocyclic tetranuclear ZnII complex as a receptor for selective dual fluorescence sensing of F− and AcO−: effect of a macrocyclic ligand
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Ennio Zangrando, Tonmoy Chakraborty, Debasis Das, Daniel Escudero, Sanchari Dasgupta, and Arghyadeep Bhattacharyya
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MECHANISM ,Chemistry, Multidisciplinary ,Imine ,Protonation ,02 engineering and technology ,010402 general chemistry ,ANTHRACENE ,01 natural sciences ,AQUEOUS-SOLUTION ,Catalysis ,ANION RECOGNITION ,chemistry.chemical_compound ,BINDING ,Materials Chemistry ,PROBE ,FLUORIDE IONS ,Detection limit ,Science & Technology ,Aqueous solution ,SENSOR ,General Chemistry ,021001 nanoscience & nanotechnology ,Combinatorial chemistry ,Fluorescence ,0104 chemical sciences ,Chemistry ,chemistry ,PORPHYRIN ,Physical Sciences ,CHEMOSENSOR ,Macrocyclic ligand ,0210 nano-technology ,Single crystal ,Fluoride - Abstract
A 48-membered macrocyclic ZnII-Schiff base complex DAS (Dual Anion Sensor) containing protonated imine has been synthesized and characterised. The single crystal X-ray structural analysis reveals a tetranuclear complex cation [Zn4(LH3)(NO3)5]2+ counterbalanced by a [Zn(NO3)4]2− anion. DAS acts as a dual anion sensor which can selectively detect fluoride and acetate in aqueous methanolic solution by change in UV-vis spectra as well as by fluorescence enhancement. A probable mechanistic pathway has been proposed and DFT calculations corroborate well with the experimental data. The calculated limit of detection for F− and AcO− ions was 0.18 and 1.98 μM, and 0.15 and 1.8 μM from UV and FL data, respectively. Interestingly, DAS behaves as an INHIBIT logic gate with F−/AcO− and H+ as inputs. To the best of our knowledge, this is the first example where a macrocyclic Zn-complex serves as an INHIBIT logic gate. Practical utility of DAS has been explored by successful detection of F− in commercially available toothpaste as well as solid state detection of F− and AcO−.
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- 2019
12. Twisted BODIPY derivative: intersystem crossing, electron spin polarization and application as a novel photodynamic therapy reagent
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Ayhan Elmali, Jianzhang Zhao, Daniel Escudero, Partha Maity, Matvey V. Fedin, Shujing Li, Ahmet Karatay, Omar F. Mohammed, Ivan V. Kurganskii, Yu Dong, Huijian Wu, and Prashant Kumar
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Boron Compounds ,Materials science ,General Physics and Astronomy ,Quantum yield ,Antineoplastic Agents ,Microbial Sensitivity Tests ,Physics, Atomic, Molecular & Chemical ,010402 general chemistry ,Photochemistry ,01 natural sciences ,law.invention ,chemistry.chemical_compound ,Delocalized electron ,law ,Humans ,Physical and Theoretical Chemistry ,Triplet state ,Electron paramagnetic resonance ,Photosensitizing Agents ,Science & Technology ,Molecular Structure ,Singlet Oxygen ,010405 organic chemistry ,Singlet oxygen ,Chemistry, Physical ,Physics ,Electron Spin Resonance Spectroscopy ,Spin–orbit interaction ,0104 chemical sciences ,Chemistry ,Intersystem crossing ,chemistry ,Photochemotherapy ,Physical Sciences ,BODIPY ,HeLa Cells - Abstract
The photophysical properties of a heavy atom-free BODIPY derivative with a twisted π-conjugated framework were studied. Efficient intersystem crossing (ISC quantum yield: 56%) and an exceptionally long-lived triplet state were observed (4.5 ms in solid polymer film matrix and 197.5 μs in solution). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy and DFT computations confirmed the delocalization of the triplet state on the whole twisted π-conjugated framework and the zero-field-splitting (ZFS) D parameter of D = -69.5 mT, which is smaller than that of 2,6-diiodoBODIPY (D = -104.6 mT). The electron spin polarization (ESP) phase pattern of the triplet state TREPR spectrum of the twisted BODIPY is (a, a, e, a, e, e), which is different from that of 2,6-diiodo BODIPY (e, e, e, a, a, a), indicating that the electron spin selectivity of the ISC of the twisted structure is different from that of the spin orbital coupling effect. According to the computed spin-orbit coupling matrix elements (0.154-1.964 cm-1), together with the matched energy of the S1/Tn states, ISC was proposed to occur via S1→T2/T3. The computational results were consistent with TREPR results on the electron spin selectivity (the overpopulation of the TY sublevel of the T1 state). The advantage of the long-lived triplet state of the twisted BODIPY was demonstrated by its efficient singlet oxygen (1O2) photosensitizing (ΦΔ = 50.0%) even under a severe hypoxia atmosphere (pO2 = 0.2%, v/v). A high light toxicity (EC50 = 1.0 μM) and low dark toxicity (EC50 = 78.5 μM) were observed for the twisted BODIPY, and thus the cellular studies demonstrate its potential as a novel potent heavy atom-free photodynamic therapy (PDT) agent. ispartof: PHYSICAL CHEMISTRY CHEMICAL PHYSICS vol:23 issue:14 pages:8641-8652 ispartof: location:England status: published
- Published
- 2021
13. Thienyl/phenyl bay-substituted perylenebisimides: Intersystem crossing and application as heavy atom-free triplet photosensitizers
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Ayhan Elmali, Daniel Escudero, Ahmet Karatay, Jianzhang Zhao, Yuqi Hou, Zhijia Wang, and Farhan Sadiq
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Technology ,Engineering, Chemical ,General Chemical Engineering ,Materials Science ,Substituent ,Quantum yield ,EXCITED-STATE ,02 engineering and technology ,Triplet state ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Perylenebisimide ,DENSITY-FUNCTIONAL THEORY ,Electron transfer ,chemistry.chemical_compound ,ENERGY-LEVELS ,Engineering ,CHARGE-TRANSFER ,Thiophene ,Materials Science, Textiles ,ELECTRON-TRANSFER ,Singlet state ,SINGLET OXYGEN GENERATION ,ACTIVATED DELAYED FLUORESCENCE ,BASIS-SETS ,PERYLENE ,Science & Technology ,Chemistry ,Singlet oxygen ,Process Chemistry and Technology ,Intersystem crossing ,021001 nanoscience & nanotechnology ,Delayed fluorescence ,0104 chemical sciences ,Chemistry, Applied ,PHOTON UP-CONVERSION ,Excited state ,Physical Sciences ,0210 nano-technology - Abstract
Different perylene-3,4:9,10-bis(dicarboximide) (abbreviated as perylenebisimides, or simply PBI) compounds (MT-PBI, DT-PBI, MP-PBI and DP-PBI) with thienyl and phenyl substituents at the bay position were prepared to study the effect of substitution on the photophysical properties, especially the intersystem crossing (ISC) efficacy. We found that the derivative with a monothienyl substituent (MT-PBI) shows efficient ISC (singlet oxygen quantum yield ΦΔ = 72%) and longer triplet state lifetime (τT = 64.4 μs) as compared to reference compounds (derivative with monophenyl substituent at bay position, MP-PBI, ΦΔ = 23% and τT = 48.5 μs). Theoretical computations reveal that the ISC efficiency is dependent on the magnitude of the spin orbit couplings (SOC) between the singlet and triplet excited states, and the SOC matrix element is up to 2 cm−1 for compound showing the highest ISC efficiency. Femtosecond transient absorption spectra show the ISC rate constant of 8 × 109 s−1 for MT-PBI, and no charge transfer exists. Photo-driven electron transfer was observed with the PBI derivatives in the presence of sacrificial electron donor triethanolamine (TEOA), and reversible formation of PBI radical anion (PBI−•) was observed, which shows absorption in the range of 600 nm–800 nm and 900 nm–1000 nm. Delayed fluorescence (P-type) in MT-PBI was also observed (τT = 31.0 μs). These finding are useful for the design of PBI-derived heavy atom-free compounds to be used as triplet photosensitizers.
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- 2021
14. Computational Protocol To Predict Anti-Kasha Emissions: The Case of Azulene Derivatives
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Koen Veys and Daniel Escudero
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Photoluminescence ,Physics, Atomic, Molecular & Chemical ,POLARIZATION PROPAGATOR ,010402 general chemistry ,Kinetic energy ,01 natural sciences ,Molecular physics ,3RD-ROW ATOMS ,Spectral line ,DENSITY-FUNCTIONAL THEORY ,chemistry.chemical_compound ,0103 physical sciences ,Radiative transfer ,QUANTUM EFFICIENCY ,ORBITAL METHODS ,Emission spectrum ,FLUORESCENCE ,Physical and Theoretical Chemistry ,Quantum ,Science & Technology ,010304 chemical physics ,Chemistry, Physical ,Physics ,GAUSSIAN-BASIS SETS ,Azulene ,0104 chemical sciences ,CORRELATED MOLECULAR CALCULATIONS ,Chemistry ,EXCITED-STATES ,chemistry ,Excited state ,Physical Sciences ,RULE - Abstract
In this contribution, we present a computational protocol to predict anti-Kasha photoluminescence. The herein developed protocol is based on state-of-the-art quantum chemical calculations and excited-state decay rate theories (i.e., thermal vibration correlation function formalism), along with appropriate kinetic models which include all relevant electronic states. This protocol is validated for a series of azulene derivatives. For this series, we have computed absorption and emission spectra for both their first and second excited states, their radiative and nonradiative rates, as well as fluorescence yields from the two different excited states. All the studied azulene derivatives are predicted to exclusively display anomalous anti-Kasha S2 emission. A quantitative agreement for the herein computed excited-state spectra, lifetimes, and fluorescence quantum yields is obtained with respect to the experimental values. Given the increasing interest in anti-Kasha emitters, we foresee that the herein developed computational protocol can be used to prescreen dyes with the desired aforementioned anomalous photoluminescence properties. ispartof: JOURNAL OF PHYSICAL CHEMISTRY A vol:124 issue:36 pages:7228-7237 ispartof: location:United States status: published
- Published
- 2020
15. A Computational Protocol to Predict Anti-Kasha Emissions: The Case of Azulene Derivatives
- Author
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Daniel Escudero and Koen Veys
- Subjects
Physics ,chemistry.chemical_compound ,Photoluminescence ,Correlation function ,chemistry ,Excited state ,Radiative transfer ,Emission spectrum ,Azulene ,Quantum ,Molecular physics ,Spectral line - Abstract
In this contribution we present a computational protocol to predict anti-Kasha photoluminescence. The herein developed protocol is based on state-of-the-art quantum chemical calculations and excited state decay rate theories (i.e., thermal vibration correlation function formalism), along with appropriate kinetic models which include all relevant electronic states. This protocol is validated for a series of azulene derivatives. For this series, we have computed absorption and emission spectra for both their first and second excited states, their radiative and non-radiative rates as well as fluorescence yields from the two different excited states. All the studied azulene derivatives are predicted to exclusively display anomalous anti-Kasha S2 emission. A quantitative agreement for the herein computed excited state spectra, lifetimes and fluorescence quantum yieldsis obtained with respect to the experimental values. Given the increasing interest on anti-Kasha emitters, we foresee that the herein developed computational protocol can be used to pre-screen dyes with the desired aforementioned anomalous photoluminescence properties.
- Published
- 2020
16. Theoretical Study of a Class of Organic D-pi-A Dyes for Polymer Solar Cells: Influence of Various pi-Spacers
- Author
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Nguyen Van Trang, Le Thi Hong Hai, Ngo Tuan Cuong, Daniel Escudero, Hue Minh Thi Nguyen, Tran Ngoc Dung, and Minh Tho Nguyen
- Subjects
Technology ,General Chemical Engineering ,LIGHT-EMITTING-DIODES ,02 engineering and technology ,DFT calculations ,01 natural sciences ,dft calculations ,chemistry.chemical_compound ,RECENT PROGRESS ,Thiophene ,lcsh:QD901-999 ,General Materials Science ,Molecular orbital ,HOMO/LUMO ,chemistry.chemical_classification ,Crystallography ,D-pi-A dyes ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,PBDTS-TZNT and PBDTSF-TZNT ,d-π-a dyes ,pbdts-tznt and pbdtsf-tznt ,PHOTOVOLTAIC MATERIALS ,Physical Sciences ,Density functional theory ,0210 nano-technology ,DTS ,CONJUGATED OLIGOMERS ,Materials science ,EFFICIENCY ,Absorption spectroscopy ,MOLECULAR DESIGN ,Materials Science ,COOLIGOMERS ,Materials Science, Multidisciplinary ,010402 general chemistry ,Polymer solar cell ,Inorganic Chemistry ,Alkyl ,dts ,Science & Technology ,PERFORMANCE ,pces ,Acceptor ,0104 chemical sciences ,chemistry ,Physical chemistry ,MORPHOLOGY ,lcsh:Crystallography ,BANDGAP ,polymer solar cells ,PCEs - Abstract
A class of D-π-A compounds that can be used as dyes for applications in polymer solar cells has theoretically been designed and studied, on the basis of the dyes recently shown by experiment to have the highest power conversion efficiency (PCE), namely the poly[4,8-bis(5-(2-butylhexylthio)thiophen-2-yl)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-TZNT] (PBDTS-TZNT) and poly[4,8-bis(4-fluoro-5-(2-butylhexylthio)thiophen-2-yl)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-TZNT] (PBDTSF-TZNT) substances. Electronic structure theory computations were carried out with density functional theory and time-dependent density functional theory methods in conjunction with the 6−311G (d, p) basis set. The PBDTS donor and the TZNT (naphtho[1,2-c:5,6-c]bis(2-octyl-[1,2,3]triazole)) acceptor components were established from the original substances upon replacement of long alkyl groups within the thiophene and azole rings with methyl groups. In particular, the effects of several π-spacers were investigated. The calculated results confirmed that dithieno[3,2-b:2′,3′-d] silole (DTS) acts as an excellent π-linker, even better than the thiophene bridge in the original substances in terms of well-known criteria. Indeed, a PBDTS-DTS-TZNT combination forms a D-π-A substance that has a flatter structure, more rigidity in going from the neutral to the cationic form, and a better conjugation than the original compounds. The highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap of such a D-π-A substance becomes smaller and its absorption spectrum is more intense and red-shifted, which enhances the intramolecular charge transfer and makes it a promising candidate to attain higher PCEs.
- Published
- 2020
17. Red Thermally Activated Delayed Fluorescence and the Intersystem Crossing Mechanisms in Compact Naphthalimide–Phenothiazine Electron Donor/Acceptor Dyads
- Author
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Geliang Tang, Daniel Escudero, Wenbo Yang, Jianzhang Zhao, Qingyun Liu, A. A. Sukhanov, Violeta K. Voronkova, Zhijia Wang, Denis Jacquemin, Mariangela Di Donato, Fudan University [Shanghai], European Laboratory for Non-Linear Spectroscopy (LENS), Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Technology ,PI-A ,Luminescence ,ANNIHILATION UP-CONVERSION ,TRIPLET EXCITED-STATE ,Materials Science ,Electron donor ,Materials Science, Multidisciplinary ,02 engineering and technology ,spin dynamics ,010402 general chemistry ,Photochemistry ,DONOR ,01 natural sciences ,Quantum mechanics ,Fluorescence ,Absorption ,chemistry.chemical_compound ,Phenothiazine ,Physical and Theoretical Chemistry ,Nanoscience & Nanotechnology ,PARAMAGNETIC-RES ,Science & Technology ,SINGLET OXYGEN ,[PHYS.PHYS]Physics [physics]/Physics [physics] ,Chemistry, Physical ,INTRAMOLECULAR CHARGE-TRANSFER ,charge transfer ,021001 nanoscience & nanotechnology ,Acceptor ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Coupling (electronics) ,Chemistry ,General Energy ,Intersystem crossing ,chemistry ,time resolved spectroscopy ,Physical Sciences ,Solvents ,Science & Technology - Other Topics ,METAL-COMPLEXES ,0210 nano-technology ,ENERGY-TRANSFER ,TIME-RESOLVED EPR - Abstract
International audience; Controlling the electronic coupling between electron donor and acceptor subunits in a dyad is pivotal for the development of novel organic materials, for instance, thermally activated delayed fluorescence (TADF) materials and triplet photosensitizers. Herein, we prepared two compact electron donor/acceptor dyads based on phenothiazine (PTZ) and naphthalimide (NI) with different conformation restrictions induced by the C–N (NI-N-PTZ) or C–C (NI-C-PTZ) linkers. The effect of electronic coupling (matrix elements, VDA) on the photophysical properties, especially the intersystem crossing (ISC) and the TADF, were investigated. NI-C-PTZ shows stronger ground-state electronic coupling (VDA = 2548 cm–1) compared to NI-N-PTZ (VDA = 870 cm–1). TADF was observed only for NI-N-PTZ due to its smaller electronic coupling. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy indicated the presence two triplet excited states and three ISC mechanisms in NI-N-PTZ with different electron spin polarizations (ESP): radical pair ISC (RP-ISC) and spin–orbital charge transfer ISC (SOCT-ISC) for one triplet state, and spin–orbital coupling ISC (SO-ISC) for another. Moreover, for the second one, an inversion of the electron spin polarization (ESP) was observed at 0.5–1.1 μs delay time. NI-N-PTZ represents a rare example for compact electron donor/acceptor dyad showing TADF emission in the red spectral region.
- Published
- 2019
18. Photoinduced Energy and Electron Transfer Between a Photoactive Cage Based on a Thermally Activate Delayed Fluorescence Ligand and Encapsulated Fluorescent Dyes
- Author
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Daniel Escudero, Denis Jacquemin, Diego Rota Martir, Stuart L. Warriner, Eli Zysman-Colman, Antonella Pizzolante, 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), and University of St Andrews [Scotland]
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010405 organic chemistry ,Ligand ,Energy Engineering and Power Technology ,chemistry.chemical_element ,010402 general chemistry ,Photochemistry ,7. Clean energy ,01 natural sciences ,Fluorescence ,Photoinduced electron transfer ,0104 chemical sciences ,Electron transfer ,chemistry.chemical_compound ,chemistry ,Materials Chemistry ,Electrochemistry ,Rose bengal ,[CHIM]Chemical Sciences ,Chemical Engineering (miscellaneous) ,Molecule ,Electrical and Electronic Engineering ,Luminescence ,Palladium - Abstract
The vast majority of polyhedral assemblies prepared by combining organic bent ligands and ``photophysically innocent'' palladium(II) metal ions are nonemissive. We report here a simple strategy to switch on the luminescence properties of a polyhedral assembly by combining a thermally activated delayed fluorescence (TADF) organic emitter based on a dipyridylcarbazole ligand scaffold with Pd2+ ions, giving rise to a luminescent Pd6L12 molecular cube. The assembly is capable of encapsulating within its cavity up to three molecules per cage of fluorescein, in its neutral lactone form, and up to two molecules of Rose Bengal in its dianionic quinoidal form. Photoinduced electron transfer (PeT) between the photoactive cage and the encapsulated Fluorescein and photoinduced energy transfer (PET) from the cage to encapsulated Rose Bengal have been observed by steady-state and time-resolved emission spectroscopy.
- Published
- 2018
19. Unexpected Nucleophilic Substitution Reaction of BODIPY: Preparation of the BODIPY-TEMPO Triad Showing Radical-Enhanced Intersystem Crossing
- Author
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Kejing Xu, Yingjie Zhao, Jianzhang Zhao, Wei Ji, Denis Jacquemin, Daniel Escudero, Violeta K. Voronkova, Xiaojun Peng, and A. A. Sukhanov
- Subjects
010405 organic chemistry ,Organic Chemistry ,Triad (anatomy) ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Photon upconversion ,0104 chemical sciences ,chemistry.chemical_compound ,Intersystem crossing ,medicine.anatomical_structure ,chemistry ,Nucleophilic substitution ,medicine ,Physical and Theoretical Chemistry ,BODIPY ,Luminescence - Published
- 2018
20. A Deep Insight into the Photoluminescence Properties of Schiff Base CdII and ZnII Complexes
- Author
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Daniel Escudero, Ishani Majumder, Prateeti Chakraborty, Chiara Massera, Debasis Das, and Sanchari Dasgupta
- Subjects
Quantum chemical ,Photoluminescence ,Schiff base ,010405 organic chemistry ,Stereochemistry ,Chemistry ,Ligand ,Solid-state ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,3. Good health ,law.invention ,Inorganic Chemistry ,chemistry.chemical_compound ,law ,Physical and Theoretical Chemistry ,Crystallization ,Dicyanamide - Abstract
A tridentate N,N,O donor ligand 2,4-dichloro-2-[(2-piperazine-4-yl-ethylimino)-methyl]-phenol (HL) was designed, and eight new ZnII and CdII complexes, namely, [Zn(LH)(SCN)2] (1), [Zn(LH)(N3)2] (2), [Zn(LH)(NO2)2] (3), [Zn(LH)(dca)(OAc)] (4), [Cd2(LH)2(SCN)4] (5), [Cd(LH)(N3)2] (6), [Cd(LH)(NO2)2] (7), and [Cd(LH)(dca)(OAc)] (8) [where dca = dicyanamide anion] were synthesized. Five of them (1, 2, 4, 5, 7) were structurally characterized through single-crystal X-ray diffraction analysis. H-Bonding interactions are found to be the major stabilizing factor for crystallization in the solid state. Experimental and computational studies were performed in cooperation to provide a rationalization of the photoluminescence properties of those complexes. The quantum yields are anion-dependent, with enhanced efficiencies in the following order: LH < Cd-SCN(5) < Cd-dca(8) < Cd–N3(6) < Cd-NO2(7) < Zn-dca(4) < Zn–N3(2) < ZnNO2(3) < ZnSCN(1). By using quantum chemical calculations we rationalized the above trends. Moreo...
- Published
- 2017
21. Phenyl- and Pyrazolyl-Functionalized Pyrimidine: Versatile Chromophore of Bis-Tridentate Ir(III) Phosphors for Organic Light-Emitting Diodes
- Author
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Wei-Cheng Li, Yi-Kuang Chen, Chih-Hao Chang, Dian Luo, Yun Chi, Ling-Yang Hsu, Alex K.-Y. Jen, Yi-Ning Lai, Hsin-Hung Kuo, and Daniel Escudero
- Subjects
Technology ,Materials science ,General Chemical Engineering ,Materials Science ,EFFICIENCY ROLL-OFF ,FABRICATION ,Phosphor ,Materials Science, Multidisciplinary ,EMITTERS PHOTOPHYSICS ,02 engineering and technology ,Pyrazole ,010402 general chemistry ,Photochemistry ,01 natural sciences ,chemistry.chemical_compound ,Materials Chemistry ,OLED ,ELECTROLUMINESCENCE ,IRIDIUM(III) COMPLEXES ,Science & Technology ,Chemistry, Physical ,Photodissociation ,General Chemistry ,Chromophore ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Pincer movement ,Chemistry ,SKY-BLUE ,chemistry ,Physical Sciences ,Density functional theory ,HOST MATERIALS ,BLUE PHOSPHORESCENCE ,LIGAND ,0210 nano-technology ,Carbene ,TRIPLET ENERGY-LEVEL - Abstract
There is growing interest in the bis-tridentate Ir(III) emitters as they are expected to display both improved emission efficiency and improved photostability. Herein, we turned to the new emitters m2h-1–3 and m6h-1–3, bearing a pincer carbene ancillary and a chromophoric chelate derived from judiciously selected phenyl-pyrimidine-pyrazole entities (pzm2hF)H2 and (pzm6hF)H2, which differ in terms of the location of phenyl and pyrazole substituents on the central pyrimidine. Density functional theory calculations revealed a notable change in the spin density distribution from the pyrimidine-pyrazolate entity in m2h to the pyrimidine-phenyl fragment in m6h. As a consequence, the m6h emitters exhibited both shortened emission lifetimes and improved stabilities during extensive photolysis in solution, while corresponding organic light-emitting diodes (OLEDs) doped with green-emitting m6h-1 and sky-blue-emitting m6h-2 and m6h-3 exhibited external quantum efficiencies of 17.6, 15.9, and 17.6%, respectively, sup...
- Published
- 2019
22. Revising Intramolecular Photoinduced Electron Transfer (PET) from First-Principles
- Author
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Daniel Escudero, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Photoluminescence ,Fluorophore ,010405 organic chemistry ,Chemistry ,Nanotechnology ,General Medicine ,General Chemistry ,010402 general chemistry ,7. Clean energy ,01 natural sciences ,Fluorescence ,Photoinduced electron transfer ,0104 chemical sciences ,Artificial photosynthesis ,chemistry.chemical_compound ,Electron transfer ,Intramolecular force ,[CHIM]Chemical Sciences ,Excitation - Abstract
Photoinduced electron transfer (PET) plays relevant roles in many areas of chemistry, including charge separation processes in photovoltaics, natural and artificial photosynthesis, and photoluminescence sensors and switches. As in many other photochemical scenarios, the structural and energetic factors play relevant roles in determining the rates and efficiencies of PET and its competitive photodeactivation processes. Particularly, in the field of fluorescent sensors and switches, intramolecular PET is believed (in many cases without compelling experimental proof) to be responsible of the quench of fluorescence. There is an increasing experimental interest in fluorophore's molecular design and on achieving optimal excitation/emission spectra, excitation coefficients, and fluorescence quantum yields (importantly for bioimaging purposes), but less efforts are devoted to fundamental mechanistic studies. In this Account, I revise the origins of the fluorescence quenching in some of these systems with state-of-the-art quantum chemical tools. These studies go beyond the common strategy of analyzing frontier orbital energy diagrams and performing PET thermodynamics calculations. Instead, the potential energy surfaces (PESs) of the lowest-lying excited states are explored with time-dependent density functional theory (TD-DFT) and complete active space self-consistent field (CASSCF) calculations and the radiative and nonradiative decay rates from the involved excited states are computed from first-principles using a thermal vibration correlation function formalism. With such a strategy, this work reveals the real origins of the fluorescence quenching, herein entitled as dark-state quenching. Dark states (those that do not absorb or emit light) are often elusive to experiments and thus, computational investigations can provide novel insights into the actual photodeactivation mechanisms. The success of the dark-state quenching mechanism is demonstrated for a wide variety of fluorescent probes, including proton, cation and anion targets. Furthermore, this mechanism provides a general picture of the fluorescence quenching which englobes intramolecular charge-transfer (ICT), ratiometric quenching, and those radiationless mechanisms believed to be originated by PET. Finally, this Account provides for the first time a computational protocol to quantitatively estimate this phenomenon and provides the ingredients for the optimal design of fluorescent probes from first principles.
- Published
- 2016
23. Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems
- Author
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Douglas Philp, Tamara Kosikova, Daniel M. Dawson, David B. Cordes, Sharon E. Ashbrook, Ifor D. W. Samuel, Eli Zysman-Colman, Daniel Escudero, Gordon J. Hedley, Diego Rota Martir, Alexandra M. Z. Slawin, Denis Jacquemin, University of St Andrews [Scotland], 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), School of Chemistry, SUPA School of Physics and Astronomy [University of St Andrews], University of St Andrews [Scotland]-Scottish Universities Physics Alliance (SUPA), EPSRC, European Research Council, University of St Andrews. School of Chemistry, University of St Andrews. Organic Semiconductor Centre, University of St Andrews. School of Physics and Astronomy, University of St Andrews. EaSTCHEM, University of St Andrews. Biomedical Sciences Research Complex, and University of St Andrews. Condensed Matter Physics
- Subjects
010405 organic chemistry ,Stereochemistry ,Supramolecular chemistry ,chemistry.chemical_element ,DAS ,Crystal structure ,QD Chemistry ,010402 general chemistry ,01 natural sciences ,Porphyrin ,0104 chemical sciences ,Inorganic Chemistry ,NMR spectra database ,chemistry.chemical_compound ,Crystallography ,chemistry ,Pyridine ,Proton NMR ,[CHIM]Chemical Sciences ,QD ,Density functional theory ,Iridium - Abstract
EZ-C acknowledges the University of St Andrews for financial support. IDWS acknowledges support from EPSRC (EP/J009016) and the European Research Council (grant 321305). IDWS also acknowledges support from a Royal Society Wolfson research merit award. DJ acknowledges the European Research Council (grant: 278845) and the RFI Lumomat for financial support. We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(III) complexes of the form of [Ir(C^N)2(N^N)]PF6 (where C^N is mesppy = 2-phenyl-4-mesitylpyridinato and dFmesppy = 2-(4,6-difluorophenyl)-4-mesitylpyridinato and N^N is 4,4':2',2'':4'',4'''-quaterpyridine, qpy) and zinc tetraphenylporphyrin (ZnTPP), assembled through non-covalent interactions between the distal pyridine moieties of the qpy ligand located on the iridium complex and the zinc of the ZnTPP. The assemblies have been comprehensively characterized by a series of analytical techniques (1H NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature 1H NMR spectroscopy) and the crystal structures have been elucidated by X-ray diffraction. The optoelectronic properties of the assemblies and the electronic interaction between the iridium and porphyrin chromophoric units have been explored with detailed photophysical measurements, supported by time-dependent density functional theory (TD-DFT) calculations. Postprint
- Published
- 2016
24. Modulation of Solid‐State Aggregation of Square‐Planar Pt(II) Based Emitters: Enabling Highly Efficient Deep‐Red/Near Infrared Electroluminescence
- Author
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Nawee Kungwan, Wen-Cheng Chen, Yun Chi, Chattarika Sukpattanacharoen, Hsiu-Fu Hsu, Wei-Hsiang Chan, Chun-Chi Huang, Dong Shen, Wen-Yi Hung, Daniel Escudero, and Chun-Sing Lee
- Subjects
Technology ,Materials science ,Chemistry, Multidisciplinary ,Materials Science ,LIGHT-EMITTING-DIODES ,Materials Science, Multidisciplinary ,Electroluminescence ,EXTERNAL QUANTUM EFFICIENCY ,Physics, Applied ,law.invention ,Biomaterials ,Planar ,law ,solid-state aggregation ,Electrochemistry ,OLED ,Nanoscience & Nanotechnology ,near-infrared phosphorescent emitters ,ACTIVATED DELAYED FLUORESCENCE ,STACKING ,Science & Technology ,Chemistry, Physical ,business.industry ,Physics ,PHOSPHORESCENCE ,organic light-emitting diodes ,RED ,Condensed Matter Physics ,Electronic, Optical and Magnetic Materials ,Chemistry ,PLATINUM(II) COMPLEXES ,Physics, Condensed Matter ,trimers ,Modulation ,Physical Sciences ,LUMINESCENCE ,Science & Technology - Other Topics ,Optoelectronics ,Quantum efficiency ,LIGAND ,EMISSION ,business ,Luminescence ,Phosphorescence ,Pt(II) complexes ,Light-emitting diode - Abstract
ispartof: ADVANCED FUNCTIONAL MATERIALS vol:30 issue:25 status: published
- Published
- 2020
25. Facial and Meridional Isomers of Tris(bidentate) Ir(III) Complexes: Unravelling Their Different Excited State Reactivity
- Author
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Daniel Escudero, Sylvio Arroliga-Rocha, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Tris ,Denticity ,FOS: Physical sciences ,Stereoisomerism ,Zonal and meridional ,Phosphor ,02 engineering and technology ,010402 general chemistry ,Photochemistry ,01 natural sciences ,DEGRADATION MECHANISMS ,Inorganic Chemistry ,chemistry.chemical_compound ,Physics - Chemical Physics ,Chemistry, Inorganic & Nuclear ,[CHIM]Chemical Sciences ,Reactivity (chemistry) ,Physical and Theoretical Chemistry ,DIODES ,LIGHT-EMITTING DEVICES ,Chemical Physics (physics.chem-ph) ,IRIDIUM(III) COMPLEXES ,ISOMERIZATION ,Science & Technology ,021001 nanoscience & nanotechnology ,SMALL-MOLECULE ,0104 chemical sciences ,Chemistry ,chemistry ,Excited state ,DENSITY ,Physical Sciences ,0210 nano-technology ,Phosphorescence - Abstract
The use of tris(bidentate) Ir(III) complexes as light active components in phosphorescent organic light-emitting diodes (PhOLEDs) is currently the state-of-the-art technology to attain long-lasting and highly performing devices. Still, further improvements of their operational lifetimes are required for their practical use in lighting and displays. Facial/meridional stereoisomerism of the tris(bidentate) Ir(III) architectures strongly influences their emissive properties and thereto their PhOLEDs performances and operational device stabilities. This work underpins at the first-principles level the different excited state reactivities of facial and meridional stereoisomers of a series of tris(bidentate) Ir(III) complexes, which is found to originate in the presence of distinct triplet metal-centered (3MC) deactivation pathways. These deactivation pathways are herein presented for the first time for the meridional isomers. Finally, we propose some phosphor design strategies. ispartof: INORGANIC CHEMISTRY vol:57 issue:19 pages:12106-12112 ispartof: location:United States status: published
- Published
- 2018
26. A family of [ Cu2], [ Cu4] and [ Cu5] aggregates: alteration of reaction conditions, ancillary bridges and capping anions
- Author
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Daniel Escudero, Gavin A. Craig, Manisha Das, Mark Murrie, Debashis Ray, Antonio Frontera, Department of Chemistry [IIT Kharagpur], Indian Institute of Technology Kharagpur (IIT Kharagpur), Departament de Quimica Inorganica, Universitat de Barcelona (UB), 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), Département de cardiologie, CHU Bordeaux [Bordeaux]-Hôpital Haut-Lévêque [CHU Bordeaux], CHU Bordeaux [Bordeaux], and Department of Chemistry, Indian Institute of Technology
- Subjects
Reaction conditions ,010405 organic chemistry ,Ligand ,Condensation ,chemistry.chemical_element ,Infrared spectroscopy ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Copper ,Catalysis ,0104 chemical sciences ,Ion ,Crystallography ,Perchlorate ,chemistry.chemical_compound ,chemistry ,Octahedron ,Materials Chemistry ,[CHIM]Chemical Sciences ,QD - Abstract
The phenoxido-bridged [Cu-2] complex [Cu-2(-H(4)L1)(-OH)((1,3)-NO3)(NO3)(OH2)]H2O (1) and its hierarchical [Cu-4] and [Cu-5] assemblies [Cu-4(-H(4)L1)(2)(-OH)(2)((1,3)-ClO4)(OH2)(2)](ClO4)(3)2H(2)O (2) and [Cu-5(-H(4)L1)(2)((3)-OH)(2)((1,3)-O2CCF3)(2)(O2CCF3)(2)](CF3COO)(2) (3) were obtained from the reactions of H(5)L1 (2,6-bis-\(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl\-4-methylphen ol) with three copper(ii) salts. The available NO3-, ClO4- and CF3COO- ions have been trapped for spontaneous' anion-directed self-assembly' reactions. All the synthesized complexes contain the [Cu-2(-H(4)L1)(-OH)](2+) fragment, prone to assemble and crystallize [Cu-4] and [Cu-5] complexes under varying reaction conditions. They were characterized by UV-vis and IR spectroscopy, X-ray diffraction analysis and magnetic studies. A change from NO3- to ClO4- and CF3COO- results in different courses of reactions based on Cu-2(-H(4)L1) fragments. Binding of NO3- provided 1 as an isolated [Cu-2] complex by trapping the reactive fragment. In 2 a perchlorate ligand, in the (1,3)-binding mode, has been realized as a solitary support for the condensation of two Cu-2(-H(4)L1) fragments. The \Cu-5((3)-OH)(2)((1,3)-O2CCF3)(2)\(6+) constellation in 3 contains five Cu-II centers with a unique Z-in distorted octahedral one at the central position. Binding of different anions to the copper(ii) centers controls the nuclearity of the reaction products and tuning of the self-aggregation process within the same ligand environment (-H(4)L1(-)). The magnetic properties of the compounds have been studied both experimentally and using DFT calculations, revealing moderate to strong antiferromagnetic coupling in all aggregates.
- Published
- 2018
27. Thermal equilibration between excited states or solvent effects: unveiling the origins of anomalous emissions in heteroleptic Ru( ii ) complexes
- Author
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Daniel Escudero, Denis Jacquemin, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Chemical Physics (physics.chem-ph) ,Materials science ,Photoluminescence ,General Physics and Astronomy ,FOS: Physical sciences ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Solvent ,chemistry.chemical_compound ,chemistry ,Relaxation effect ,Excited state ,Physics - Chemical Physics ,Thermal equilibration ,Physical chemistry ,[CHIM]Chemical Sciences ,Physical and Theoretical Chemistry ,Triphenylphosphine ,Solvent effects ,0210 nano-technology ,Phosphorescence - Abstract
International audience; In this manuscript we present a computational study on the photoluminescence properties of several heteroleptic [Ru(H)(CO)(N^N)(tpp)2]+ complexes (tpp = triphenylphosphine). A special focus is set on disentangling the temperature-dependent emissive properties. Experimentally, when cooling a solution of [Ru(H)(CO)(dmphen)(tpp)2]+ (dmphen = 5,6-dimethyl-1,10-phenanthroline) from room to cryogenic temperature, a partial emission switch from metal-to-ligand charge transfer (3MLCT) to ligand-centered (3LC) phosphorescence is observed, resulting in dual photoluminescence. Two different origins of the anomalous emissions are possible, i.e., thermal equilibration between electronically excited states or different excited state solvent relaxation effects. Our calculations are in favor of the thermally equilibrated scenario. This computational investigation highlights the importance of controlling the temperature-dependent emissive behavior for optoelectronic applications.
- Published
- 2018
28. A luminescent [Pd4Ru8](24+) supramolecular cage
- Author
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Stuart L. Warriner, Daniel Escudero, Alexandra M. Z. Slawin, Diego Rota Martir, David B. Cordes, Denis Jacquemin, Eli Zysman-Colman, University of St Andrews [Scotland], Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Materials science ,010405 organic chemistry ,Metals and Alloys ,Supramolecular chemistry ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,3. Good health ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Crystallography ,Bipyridine ,chemistry.chemical_compound ,chemistry ,Materials Chemistry ,Ceramics and Composites ,[CHIM]Chemical Sciences ,Emission spectrum ,Cage ,Phosphorescence ,Luminescence - Abstract
A phosphorescent cage of the form [Pd4Ru8](24+) is reported. The cage was formed using the metalloligand [Ru(dtbubpy)(2)(qpy)](2+), where qpy = 4,4': 2',2 `': 4 `',4'''-quaterpyridine and dtbubpy = 4,4'-di-tert-butyl-2,2'-bipyridine. The cage has been characterised by NMR, ESI-MS, TEM and X-ray diffraction analyses and its emission properties elucidated by steady-state and time-resolved emission spectroscopy.
- Published
- 2018
29. Electronic Structure of N2P2 Four-Membered Rings and the Effect of Their Ligand Coordination to M(CO)5 (Cr, Mo, and W)
- Author
-
Daniel Escudero, Antonio Frontera, Antonio Bauzá, and Rainer Streubel
- Subjects
Inorganic Chemistry ,Crystallography ,Character (mathematics) ,Computational chemistry ,Chemistry ,Ligand ,Organic Chemistry ,Ab initio ,Electronic structure ,Physical and Theoretical Chemistry ,Antibonding molecular orbital ,Ring (chemistry) - Abstract
In this article the biradicaloid character of the ground-state structures of N2P2R2 (R = CH3) rings is studied using the DFT and CASSCF methods, and a satisfactory agreement of the B3LYP functional and CASSCF(6,6) ab initio method has been found. In order to obtain an adequate description of the biradicaloid character, we have combined two criteria: (i) singlet–triplet energy gaps and (ii) relative values of the occupation numbers for bonding and antibonding orbitals associated with the radical sites. We have analyzed how the biradicaloid character of the N2P2R2 ring changes upon coordination to M(CO)5 (M = Cr, Mo, and W) at the B3LYP/6-311+G* level of theory. Interestingly, in some cases the biradicaloid character increases dramatically upon complexation of the N2P2R2 ligands.
- Published
- 2014
30. On the Reactivity of Tetrakis(trifluoromethyl)cyclopentadienone towards Carbon-Based Lewis Bases
- Author
-
Manuel Alcarazo, Walter Thiel, Jörg Rust, Sigrid Holle, Daniel Escudero, and Blanca Inés
- Subjects
Steric effects ,chemistry.chemical_classification ,Trifluoromethyl ,Ketone ,Bicyclic molecule ,Organic Chemistry ,General Chemistry ,Medicinal chemistry ,Catalysis ,Adduct ,chemistry.chemical_compound ,Nucleophile ,chemistry ,Organic chemistry ,Reactivity (chemistry) ,Lewis acids and bases - Abstract
The reactivitiy of tetrakis(trifluoromethyl)cyclopentadienone towards different C-based Lewis bases, such as N-heterocyclic carbenes (NHC), ylides and isonitriles, are reported. While sterically not hindered carbenes were found to yield kinetic adducts by regiospecific nucleophilic attack at the position adjacent to the carbonyl group of the ketone, bulkier nucleophiles afforded the thermodynamically more stable O-bridged zwitterions. Interestingly, isonitriles were found to dimerize and trimerize under the same reaction conditions, forming bicyclic products that evolve differently depending on the nature of the substituents.
- Published
- 2014
31. Photoinduced electron transfer in supramolecular ruthenium-porphyrin assemblies
- Author
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Daniel Escudero, Denis Jacquemin, Diego Rota Martir, Eli Zysman-Colman, Mattia Averardi, EPSRC, University of St Andrews. School of Chemistry, University of St Andrews. Organic Semiconductor Centre, University of St Andrews. EaSTCHEM, 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 Nantes (UN), and University of St Andrews [Scotland]
- Subjects
010405 organic chemistry ,Ligand ,Supramolecular chemistry ,chemistry.chemical_element ,DAS ,010402 general chemistry ,Photochemistry ,QD Chemistry ,01 natural sciences ,Porphyrin ,Photoinduced electron transfer ,0104 chemical sciences ,Ruthenium ,Inorganic Chemistry ,Photoexcitation ,chemistry.chemical_compound ,Electron transfer ,chemistry ,Pyridine ,Organic chemistry ,[CHIM]Chemical Sciences ,QD - Abstract
EZ-C acknowledges the University of St Andrews and EPSRC (EP/M02105X/1) for financial support. DE thanks funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 700961. DJ acknowledges the European Research Council (grant: 278845) and the RFI Lumomat for financial support. We present dynamic supramolecular systems composed of a Ru(II) complex of the form of [Ru(dtBubpy)2(qpy)][PF6]2 (where dtBubpy is 4,4′-di-tert-butyl-2,2′-dipyridyl and qpy is 4,4':2',2'':4'',4'''-quaterpyridine) and zinc tetraphenylporphyrins (ZnTPP), through non- covalent interactions between the distal pyridine moieties of the qpy ligand the zinc of ZnTPP. The optoelectronic properties of the assemblies and the electronic interactions between the chromophoric units have been comprehensively characterized by computational investigations, and steady-state and time-resolved emission spectroscopy. Upon photoexcitation of ZnTPP, electron transfer to the ruthenium center is thermodynamically favorable and, as a result, strong emission quenching of both units occurs. Postprint
- Published
- 2017
32. The short device lifetimes of blue PhOLEDs: insights into the photostability of blue Ir(III) complexes
- Author
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Daniel Escudero, Denis Jacquemin, Université de Nantes (UN), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Materials science ,Dopant ,business.industry ,Phosphor ,Nanotechnology ,02 engineering and technology ,General Chemistry ,Electroluminescence ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,7. Clean energy ,0104 chemical sciences ,3. Good health ,Chemistry ,Excited state ,Optoelectronics ,[CHIM]Chemical Sciences ,0210 nano-technology ,business ,Phosphorescence ,Diode - Abstract
Computationally-guided blue phosphor design strategies to attain photostable complexes upon PhOLED operation., Using Ir(iii) complexes as dopants in phosphorescent organic light-emitting diodes (PhOLEDs) is the most successful strategy to attain long-lasting and highly-performant electroluminescent devices. Whilst highly efficient blue PhOLEDs are accessible, their limited operational lifetimes still restraint their practical use in lighting and displays. These short lifetimes are directly related to the low intrinsic photostability of blue Ir(iii) complexes. This work uses first principles to unveil the mechanisms of degradation of blue phosphors arising from energetically hot excited states (≅6.0 eV), and to propose a strategy for improving the stability of blue phosphors.
- Published
- 2017
33. Ultrafast Excited-State Dynamics in Cyclometalated Ir(III) Complexes Coordinated with Perylenebisimide and Its pi-Radical Anion Ligands
- Author
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Wei Ji, Wenbo Yang, Carlos E. Crespo-Hernández, Denis Jacquemin, Brennan Ashwood, Daniel Escudero, Jianzhang Zhao, 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), and Université de Nantes (UN)
- Subjects
Chemistry ,Analytical chemistry ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Ion ,General Energy ,Intersystem crossing ,Excited state ,Ultrafast laser spectroscopy ,[CHIM]Chemical Sciences ,Physical and Theoretical Chemistry ,Triplet state ,Absorption (chemistry) ,0210 nano-technology ,Spectroscopy ,Visible spectrum - Abstract
Cyclometalated Ir(III) complexes showing strong absorption of visible light and a long-lived triplet state are of particular interest as photocatalysts and photosensitizers. Steady-state and femtosecond transient absorption spectroscopy, complemented with TD-DFT computations, are used to study the ultrafast intersystem crossing (ISC) dynamics of two perylenebisimide (PBI)-containing cyclometalated Ir(III) complexes (Ir PBI and Ir NPBI). The S-1 -> T-n ISC dynamics of these complexes is ultrafast, similar to the conventional Ir(III) complexes bearing a (MLCT)-M-1 -> (MLCT)-M-3 transition. Much longer triplet decay lifetimes are observed in Ir PBI (tau(T) = 11.4 mu s) and Ir-NPBI (tau(T) = 7.9 mu s) compared to conventional Ir(III) complexes (tau(T) < 5 mu s). This can be rationalized by the character of the lowest -energy triplet excited state (T-1). In the case of the PBI-containing complexes, the T-1 is of intraligand character ((IL)-I-3), and the T-1 -> S-0 spin orbital coupling (SOC) is 3 cm(-1). This is in contrast with conventional Ir(III) complexes, where the (MLCT)-M-3 -> S-0 has SOCs of 490 cm(-1). In the presence of a typical sacrificial electron donor, triethanolamine (TEOA), the coordinated PBI ligands are transformed into their radical form under an inert atmosphere, either with or without photoexcitation. We found that the triplet-state population is decreased with formation of the radical. The doublet excited state has a lifetime in the range of 4-7 ps.
- Published
- 2017
34. Exploring the Triplet Excited State Potential Energy Surfaces of a Cyclometalated Pt(II) Complex: Is There Non-Kasha Emissive Behavior?
- Author
-
Walter Thiel and Daniel Escudero
- Subjects
Time Factors ,Molecular Structure ,Organoplatinum Compounds ,Pyridines ,Surface Properties ,Ligand ,Temperature ,Radiative decay ,Photochemistry ,Potential energy ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Excited state ,Quantum Theory ,Density functional theory ,Physical and Theoretical Chemistry ,Quadratic response ,Derivative (chemistry) - Abstract
In this Article, we address the complexity of the emissive processes of a square-planar heteroleptic Pt(II) complex bearing 2-phenylpyridine (ppy) as cyclometalated ligand and an acetylacetonate derivative (dbm) as ancillary ligand. The origins of emission were identified with the help of density functional theory (DFT) and quadratic response (QR) time-dependent (TD)-DFT calculations including spin-orbit coupling (SOC). To unveil the photodeactivation mechanisms, we explored the triplet potential energy surfaces and computed the SOCs and the radiative decay rates (kr) from possible emissive states. We find that emission likely originates from a higher-lying (3)MLCT/(3)LLCT state and not from the Kasha-like (3)MLCT/(3)LCdbm state. The temperature-dependent nonradiative deactivation mechanisms were also elucidated. The active role of metal-centered ((3)MC) triplet excited states is confirmed for these deactivation pathways.
- Published
- 2014
35. Electronic Structure of N2P2Four-Membered Rings
- Author
-
Rainer Streubel, Antonio Frontera, and Daniel Escudero
- Subjects
Character (mathematics) ,Atomic orbital ,Main group element ,Chemistry ,Ab initio quantum chemistry methods ,Ab initio ,Electronic structure ,Physical and Theoretical Chemistry ,Atomic physics ,Antibonding molecular orbital ,Wave function ,Atomic and Molecular Physics, and Optics - Abstract
The biradicaloid character of the ground-state structures of N2P2 rings is studied by using the high-level ab initio multiconfigurational CASPT2/CASSCF method. In order to obtain accurate descriptors, we combine two criteria: 1) singlet-triplet energy gaps and 2) relative values of the occupation numbers for bonding and antibonding orbitals associated with the radical sites. The singlet-triplet energy gaps, the occupation numbers of antibonding-like orbitals, and the weights of the main configuration state functions (CSFs) of the ground-state wavefunctions, that is, Ψ((1)A1), are used to derive the biradicaloid character that ranges from 10-15%.
- Published
- 2014
36. Quantum chemical modelling of Ir(III) complexes for OLEDs (Conference Presentation)
- Author
-
Daniel Escudero and Denis Jacquemin
- Subjects
Photoluminescence ,Dopant ,business.industry ,Chemistry ,Phosphor ,Electronic structure ,law.invention ,law ,Chemical physics ,OLED ,Phosphorescent organic light-emitting diode ,Optoelectronics ,Quantum efficiency ,business ,Phosphorescence - Abstract
Ir(III) complexes are often used as triplet emitter dopants in phosphorescent organic light-emitting diodes (PhOLEDs). Optimizing their photoluminescence quantum yields (PLQY) at room temperature and controlling the light-outcoupling is key to attain highly performant PhOLEDs.[1] This work demonstrates that the quantum chemical modelling of phosphors is a helpful tool to: i) attain quantitative predictions of their PLQY and ii) rationalize the amount of light-outcoupling. More in details, we show that the quantitative prediction of the PLQY of blue-to-green Ir(III) complexes can be derived exclusively from electronic structure calculations and the use of simplified kinetic models.[2] Within these models, only a few calculations are needed: computing the radiative rate from the emissive state and characterizing the potential energy surfaces of the temperature-dependent non-radiative deactivation channels. This approach is extremely beneficial for the in silico prescreening of promising deep blue PhOLED emissive materials. Finally, the accurate calculation of the singlet-triplet transition dipole moments provides important insights into the design of Ir(III) complexes with improved outcoupling factors. [1] Computational insights into the photodeactivation dynamics of phosphors for OLEDs: a perspective. D. Escudero and D. Jacquemin, Dalton Trans., 2015, 44, 8346. [2] Quantitative prediction of photoluminescence quantum yields of phosphors from first principles. D. Escudero, Chem. Sci., 2016, 7, 1262.
- Published
- 2016
37. Unveiling Photodeactivation Pathways for a New Iridium(III) Cyclometalated Complex
- Author
-
Walter Thiel, Elisabeth Holder, Michael Schäferling, Robert J. Meier, Eike Heuser, and Daniel Escudero
- Subjects
chemistry.chemical_compound ,chemistry ,Computational chemistry ,Ligand ,Excited state ,Organic Chemistry ,chemistry.chemical_element ,Density functional theory ,General Chemistry ,Iridium ,Thiazole ,ta116 ,Catalysis - Abstract
We report the synthesis and characterization of a neutral heteroleptic Ir(III) complex bearing 6-fluoro-2-phenylbenzo[d]thiazole as cyclometalating ligand and (Z)-6-(9H-carbazol-9-yl)-5-hydroxy-2,2-dimethylhex-4-en-3-one as ancillary ligand. The photodeactivation mechanisms have been elucidated through extensive density functional theory (DFT) calculations. The active role of metal-centered ((3) MC) triplet excited states in the nonradiative deactivation pathways is, for first time, confirmed in such complexes.
- Published
- 2013
38. EPR interpretation, magnetism and biological study of a Cu(II) dinuclear complex assisted by a schiff base precursor
- Author
-
Tulin Askun, Chiara Massera, Chittaranjan Sinha, Antonio Frontera, Daniel Escudero, Kuheli Das, Eugenio Garribba, Pinar Celikboyun, Belete B. Beyene, Chen-Hsiung Hung, Chiranjit Patra, Chandana Sen, Amitabha Datta, Mohamed Salah El Fallah, 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), Departament de Quimica, Universitat des Illes Balears, Dipartimento di Chimica Generale ed Inorganica, University of Parma = Università degli studi di Parma [Parme, Italie], Department of Chemistry, University of Sassari, and Fen Edebiyat Fakültesi
- Subjects
Models, Molecular ,Magnetism ,Stereochemistry ,Cell Survival ,Cytotoxicity ,Imine ,Cu(II) Complex ,Microbial Sensitivity Tests ,010402 general chemistry ,Crystallography, X-Ray ,01 natural sciences ,Biochemistry ,law.invention ,Inorganic Chemistry ,chemistry.chemical_compound ,Structure-Activity Relationship ,law ,Chlorocebus aethiops ,Organometallic Compounds ,Antiferromagnetism ,[CHIM]Chemical Sciences ,Animals ,Electron paramagnetic resonance ,Vero Cells ,Anti-Mycobacterial ,Cells, Cultured ,Schiff Bases ,Schiff base ,Dose-Response Relationship, Drug ,Molecular Structure ,010405 organic chemistry ,Ligand ,Chemistry ,Magnetic Phenomena ,Electron Spin Resonance Spectroscopy ,Temperature ,Mycobacterium tuberculosis ,Spectra ,3. Good health ,0104 chemical sciences ,Anti-Bacterial Agents ,Crystallography ,Diethylenetriamine ,Quantum Theory ,Single crystal ,Copper - Abstract
Aşkun, Tülin (Balikesir Author), "A new Cu(II) dinuclear complex, Cu2L2 (1) was afforded employing the potentially pentatentate Schiff base precursor H2L, a refluxed product of o-vanillin and diethylenetriamine in methanol. Complex 1 was systematically characterized by FTIR, UV-Vis, emission and EPR spectrometry. The single crystal X-ray diffraction analysis of 1 reveals that the copper atom exhibits a distorted square planar geometry, comprising two pairs of phenolato-O and imine-N donors from two different H2L ligands. The temperature dependent magnetic interpretation agrees with the existence of weak antiferromagnetic interactions between the bridging dinuclear Cu(II) ions. A considerable body of experimental evidence has been accumulated to elucidate the magneto-structural relationship in this dinuclear Cu(II) complex by DFT computation. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy on M. tuberculosis H37Ra (ATCC 25177) and M. tuberculosis H(37)Rv (ATCC 25618) strains. The practical applicability of the ligand and complex 1 has been examined in living cells (African Monkey Vero Cells). The MTT assay proves the non-toxicity of the probe up to 100 mg mL(-1). A new homometallic dinuclear Cu(II) complex is afforded with a tetradentate Schiff base precursor. EPR interpretation and temperature dependent magnetic studies show that complex 1 has weak antiferromagnetic coupling and DFT computation is governed to explain the magneto-structural correlation.", "Council of Scientific and Industrial Research (CSIR) New Delhi, India 01(2731)/13/ EMR-II DGICYT of Spain CTQ2014-57393-C2-1-P CSD2010-00065 "
- Published
- 2016
39. Coumarin-Phosphine-Based Smart Probes for Tracking Biologically Relevant Metal Complexes: From Theoretical to Biological Investigations
- Author
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Ewen Bodio, Denis Jacquemin, Franck Denat, Pierre Le Gendre, Catherine Paul, Christine Goze, Lucile Dondaine, Moussa Ali, Daniel Escudero, Ali Bettaieb, Philippe Richard, École pratique des hautes études ( EPHE ), Laboratoire d'Immunologie et Immunothérapie des Cancers ( LIIC ), Université de Bourgogne ( UB ) -École pratique des hautes études ( EPHE ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation ( CEISAM ), Université de Nantes ( UN ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Universitaire de France ( IUF ), Ministère de l'Éducation nationale, de l’Enseignement supérieur et de la Recherche ( M.E.N.E.S.R. ), Centre National de la Recherche Scientifique (CNRS) (ICMUB, UMR CNRS) 6302, Université de Bourgogne, Conseil Régional de Bourgogne through the 3MIM integrated project (Marquage de Molécules par les Métaux pour l'Imagerie Médicale), PARI SSTIC 1,6, COST Action TD1004, European Research Council (ERC) Marches-278845, Région des Pays de la Loire Marches-278845, European Research Council (ERC), LUMOMAT project, École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL), Laboratoire d'Immunologie et Immunothérapie des Cancers (LIIC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Bourgogne (UB), 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), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), and Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.)
- Subjects
ab-initio ,theranostics ,chemistry.chemical_element ,010402 general chemistry ,Photochemistry ,01 natural sciences ,[ CHIM ] Chemical Sciences ,Quantitative Biology::Cell Behavior ,Bioinorganic chemistry ,Inorganic Chemistry ,chemistry.chemical_compound ,[CHIM]Chemical Sciences ,Osmium ,Singlet state ,Phosphonium ,therapy ,Antitumor agents ,010405 organic chemistry ,Chemistry ,Ligand ,Fluorescence ,0104 chemical sciences ,Ruthenium ,P ligands ,agents ,Theranostic agents ,Excited state ,Fluorescent probes ,porphyrin ,Phosphine - Abstract
International audience; Ten metal-based complexes and associated ligands have been synthesized and characterized. One of the metal ligands is a coumarin-phosphine derivative, which displays tunable fluorescence properties. The fluorescence is quenched in the case of the free ligand and ruthenium and osmium complexes, whereas it is strong for the gold complexes and phosphonium derivatives. These trends were rationalized by theoretical calculations, which revealed non-radiative channels involving a dark state for the free ligands that is lower in energy than the emissive state and is responsible for the quenching of fluorescence. For the Ru-II and Os-II complexes, other non-radiative channels involving the manifold of singlet and triplet excited states may play a role. The anti-proliferative properties of all the compounds were evaluated in cancer cell lines (SW480, HCT116, MDA-MB-231 and MCF-7); higher IC50 values were obtained for gold(I) complexes, with the free ligands being only weakly cytotoxic.
- Published
- 2016
40. Singlet oxygen generation properties of isometrically dibromated thienyl-containing aza-BODIPYs
- Author
-
Daniel Escudero, Xin-Dong Jiang, Shuang Li, Denis Jacquemin, Boris Le Guennic, Lin-Jiu Xiao, 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 Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), 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), NNSFC [21542004], Program for Liaoning Excellent Talents in University [LJQ2015087], Liaoning BaiQianWan Talents Program [2015-56], State Key Laboratory of Fine Chemicals [KF1506], Public Research Foundation of Liaoning Province for the Cause of Science [2014003009], Shenyang University of Chemical Technology, European Research Council (ERC-Marches) [278845], Region des Pays de la Loire, European Research Council (ERC) [Marches-278845], 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
molecule ,thiophene ,fluorescent ,010405 organic chemistry ,Singlet oxygen ,General Physics and Astronomy ,010402 general chemistry ,Photochemistry ,chemistry ,01 natural sciences ,dyes ,0104 chemical sciences ,chemistry.chemical_compound ,Intersystem crossing ,efficient photosensitizers ,photodynamic therapy ,Computational chemistry ,[CHIM]Chemical Sciences ,Physical and Theoretical Chemistry ,density-functional theory ,td-dft ,excited-states - Abstract
International audience; Isometrically dibromated thienyl-containing aza-BODIPYs CDB-1 and BDB-2 with potential use as photosensitizers (PSs) were successfully prepared and their photophysical properties were fully characterized. Singlet oxygen generation experiments were also performed. In this regard, PS CDB-1 was found to be more effective and had about two-fold rate enhancement compared to PS BDB-2. DFT and TD-DFT calculations helped to provide insights into the distinct intersystem crossing (ISC) processes observed for CDB-1 and BDB-2.
- Published
- 2016
41. Quantitative prediction of photoluminescence quantum yields of phosphors from first principles
- Author
-
Daniel Escudero, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
- Subjects
Photoluminescence ,business.industry ,Chemistry ,Physics::Optics ,Phosphor ,02 engineering and technology ,General Chemistry ,Electronic structure ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,OLED ,Optoelectronics ,Physical chemistry ,[CHIM]Chemical Sciences ,0210 nano-technology ,business ,Quantum ,Diode - Abstract
Optimizing the photoluminescence quantum yields of Ir(III) complexes is the key to their application as phosphors in organic light-emitting diodes (OLEDs). This work demonstrates for the first time that quantitative predictions of photoluminescence quantum yields (PLQY) in a series of blue-to-green Ir(III) complexes can be derived exclusively from electronic structure calculations.
- Published
- 2016
42. Efficient Intersystem Crossing in Heavy-Atom-Free Perylenebisimide Derivatives
- Author
-
Daniel Escudero, Wenbo Yang, Ahmet Karatay, Denis Jacquemin, H. Gul Yaglioglu, Mustafa Hayvali, Chen Li, Jianzhang Zhao, Betül Küçüköz, Christoph Sonn, 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), Xi’an Institute of Optics and Precision Mechanics, and Chinese Academy of Sciences [Xi’an]
- Subjects
010405 organic chemistry ,Chemistry ,Electron donor ,Chromophore ,010402 general chemistry ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry.chemical_compound ,General Energy ,Intersystem crossing ,Ultrafast laser spectroscopy ,Atom ,Photocatalysis ,[CHIM]Chemical Sciences ,Density functional theory ,Physical and Theoretical Chemistry ,Excitation - Abstract
Efficient intersystem crossing (ISC) in heavy-atom-free organic chromophores remains rare because of the lack of strong spin-orbit coupling effects in such compounds. Finding organic chromophores with ISC ability is important for applications in several areas, e.g., photocatalysis and photodynamic therapy. Herein, we report new perylenebisimide (PBI) chromophores with tetraphenylethynyl substituents at the 2,5,8,11-positions of the PBI core (ortho-positions, not the usually reported bay-positions of PBI), which show efficient ISC without the presence of any heavy atoms. Steady-state and picosecond-nanosecond transient absorption spectroscopies as well as time-dependent density functional theory computations were used to reveal the photophysical properties. For one of the PBI derivatives, excitation wavelength-dependent ISC was observed. The efficient ISC was attributed to the S-1/S-2 −> T-n (n > 1) processes. Photochemical reduction of the PBI derivatives in the presence of a sacrificial electron donor (triethanolamine) produced a stable PBI radical anion.
- Published
- 2016
43. The Radiative Decay Rates Tune the Emissive Properties of Ruthenium(II) Polypyridyl Complexes: A Computational Study
- Author
-
Daniel Escudero, Martin D. Hager, Bobby Happ, Andreas Winter, Leticia González, and Ulrich S. Schubert
- Subjects
chemistry ,Organic Chemistry ,Radiative decay ,chemistry.chemical_element ,General Chemistry ,Solvent effects ,Photochemistry ,Biochemistry ,Ruthenium - Published
- 2012
44. Spectroscopic Properties of Azobenzene-Based pH Indicator Dyes: A Quantum Chemical and Experimental Study
- Author
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Daniel Escudero, Beate Bussemer, Gerhard J. Mohr, Sabine Trupp, Leticia González, and Publica
- Subjects
Quantum chemical ,chemistry.chemical_compound ,Azobenzene ,Absorption spectroscopy ,Chemistry ,pH indicator ,Nanotechnology ,Physical and Theoretical Chemistry ,Photochemistry ,Computer Science Applications - Abstract
The UV visible absorption spectra of six new optical sensors based on acidochromic azobenzenes have been measured and assigned with the help of quantum chemical calculations. The investigated compounds are able to monitor the pH in the range from pH 3-10. Using the hybrid density functional PBEO and including solvent effects with a polarized continuum model, the agreement between the experimental and theoretical UV/vis spectra of the dyes in their neutral and anionic forms is very good. The spectroscopic pi pi* states, responsible for the optical properties of the sensors, are described within an accuracy of 0.1 eV. Similar accuracy is demonstrated in the ne states. The pi pi* states can be assigned as a charge transfer from the aromatic pi orbital localized in the azo-phenol moiety to the antibonding pi* of the azo group. Under basic conditions, the spectrum is bathochromically shifted and more intense than in acid media. Upon substitution in the phenyl moiety, red- or blue-shifts of the UV visible bands are observed depending on whether the substituent is electron-donor or -withdrawing, respectively. These effects are stronger at high pH values and can be rationalized in terms of the stabilization and/or destabilization of the involved frontier orbitals.
- Published
- 2011
45. Self-Assembled Molecular Complexes and Coordination Polymers of CdII, Hexamine, and Monocarboxylates: Structural Analysis and Theoretical Studies of Supramolecular Interactions
- Author
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Daniel Escudero, Biswarup Sarkar, Subrata Naiya, Michael G. B. Drew, Antonio Frontera, Shantanu Hazra, and Ashutosh Ghosh
- Subjects
Denticity ,Stereochemistry ,Supramolecular chemistry ,General Chemistry ,Crystal structure ,Condensed Matter Physics ,Crystallography ,chemistry.chemical_compound ,Pentagonal bipyramidal molecular geometry ,Octahedron ,chemistry ,Molecule ,General Materials Science ,Chelation ,Carboxylate - Abstract
Four new cadmium(II) complexes [Cd2(bz)4(H2O)4(μ2-hmt)]·Hbz·H2O (1), [Cd3(bz)6(H2O)6(μ2-hmt)2]·6H2O (2), [Cd(pa)2(H2O)(μ2-hmt)]n (3), and {[Cd3(ac)6(H2O)3(μ3-hmt)2]·6H2O}n (4) with hexamine (hmt) and monocarboxylate ions, benzoate (bz), phenylacetate (pa), or acetate (ac) have been synthesized and characterized structurally. Structure determinations reveal that 1 is dinuclear, 2 is trinuclear, 3 is a one-dimensional (1D) infinite chain, and 4 is a two-dimensional (2D) polymer with fused hexagonal rings consisting of CdII and hmt. All the CdII atoms in the four complexes (except one CdII in 2) possess seven-coordinate pentagonal bipyramidal geometry with the various chelating bidentate carboxylate groups in equatorial sites. One of the CdII ions in 2, a complex that contains two monodentate carboxylates is in a distorted octahedral environment. The bridging mode of hmt is μ2- in complexes 1−3 but is μ3- in complex 4. In all complexes, there are significant numbers of H-bonds, C−H/π, and π−π interactions wh...
- Published
- 2010
46. Mechanistic studies on the alcoholysis and aminolysis of [(MeZn)2{μ-N(H)tBu}{μ-N(CH2Py)2}]
- Author
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Helmar Görls, Julia Richthof, Leticia González, Daniel Escudero, Matthias Westerhausen, and Marcel Kahnes
- Subjects
Trimethylsilyl ,Stereochemistry ,Organic Chemistry ,Dimethylzinc ,chemistry.chemical_element ,Zinc ,Methoxide ,Biochemistry ,Medicinal chemistry ,Inorganic Chemistry ,chemistry.chemical_compound ,Aminolysis ,chemistry ,Amide ,Materials Chemistry ,Moiety ,Amine gas treating ,Physical and Theoretical Chemistry - Abstract
The reaction of bis(2-pyridylmethyl)amine (II) with t-butylamine and dimethylzinc gives the heteroleptic [(MeZn)2{μ-N(H)tBu}{μ-N(CH2Py)2}] (1). Stoichiometric alcoholysis of 1 with methanol leads to the exchange of the μ-N(H)tBu moiety. Almost quantitatively the corresponding methoxide [(MeZn)2(μ-OMe){μ-N(CH2Py)2}] (2) is formed. Alternatively bis(alkylzinc)methoxide-bis(2-pyridylmethyl)amides (Alkyl = methyl (2), bis(trimethylsilyl)methyl) (3)) are also accessible by direct zincation of bis(2-pyridylmethyl)amine (II) and methanol with dialkylzinc regardless of the bulkiness of the alkyl groups. Extensive DFT calculations on the alcoholysis mechanism reveal the preferential insertion of methanol into a zinc amide bond rather than the cleavage of zinc carbon bonds. An intermediate with a Zn[μ-(MeO⋯H⋯NHR)]Zn functionality is predicted. Aminolyis of 1 with t-butylamine leads to intermediates with Zn[μ-(RNH ⋯ H ⋯ NHR)]Zn functionalities, respectively. We were able to detect the latter by 1H NMR spectroscopy. The aminolysis of 1 with an excess of phenylamine results in a partial decomposition of the complex leading to the hexanuclear amide [{Zn(μ-N(H)Ph)}{MeZn(μ-N(H)Ph)}2{μ-N(CH2Py)2}]2 (4). Compound 2 is able to cleave silicon grease when dissolved in t-butylamine yielding [(MeZn)2{μ-N(CH2Py)2}2Zn{μ-(OMe2Si)2O}] (5). The X-ray structures of complexes 1–5 are discussed.
- Published
- 2010
47. Cooperativity effects between non-covalent interactions: Are they important for Z-DNA stability?
- Author
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Pere M. Deyà, Daniel Escudero, Antonio Frontera, David Quiñonero, and Carolina Estarellas
- Subjects
chemistry.chemical_classification ,Z-DNA ,chemistry ,Ab initio quantum chemistry methods ,Computational chemistry ,Nucleic acid ,Stacking ,General Physics and Astronomy ,Non-covalent interactions ,Cooperativity ,Crystal structure ,Physical and Theoretical Chemistry ,Stability (probability) - Abstract
We have analyzed the non-covalent interactions observed in the Z-DNA structure by examining structures retrieved from the nucleic database (NDB) and by using high level ab initio calculations (RI-MP2/aug-cc-pVTZ). We have found interesting cooperativity effects between the non-covalent interactions involved, which are important in giving stability to the Z-DNA.
- Published
- 2010
48. Phenyl-1H-[1,2,3]triazoles as New Cyclometalating Ligands for Iridium(III) Complexes
- Author
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Daniel Escudero, Ulrich S. Schubert, Christoph Ulbricht, Andreas Winter, Leticia González, Christian Friebe, Beatrice Beyer, and Chemical Engineering and Chemistry
- Subjects
Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Ligand ,Organic Chemistry ,Triazole ,chemistry.chemical_element ,Density functional theory ,Iridium ,Physical and Theoretical Chemistry ,Electrochemistry ,Combinatorial chemistry - Abstract
We report on the synthesis and characterization of bis-cyclometalated iridium(III) complexes with 4-phenyl-1H-[1,2,3]triazole, synthesized via a "click"-chemistry approach, as a new type of cyclometalating ligand. The photophysical and electrochemical properties of these complexes are investigated experimentally as well as theoretically by using density functional theory. The properties of these new complexes are compared to their known 2-phenylpyridinato analogues. The emission of the herein described complexes is clearly influenced by the applied ancillary ligand and can be adjusted over a broad range of frequencies. The results indicate that the phenyl-1H-[1,2,3]triazole ligands in general cause a spectral blue shift.
- Published
- 2009
49. Anion–π, Lone‐Pair–π, π–π and Hydrogen‐Bonding Interactions in a Cu II Complex of 2‐Picolinate and Protonated 4,4′‐Bipyridine: Crystal Structure and Theoretical Studies
- Author
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Antonio Frontera, Chaitali Biswas, Daniel Escudero, Ashutosh Ghosh, and Michael G. B. Drew
- Subjects
chemistry.chemical_classification ,Ring (chemistry) ,4,4'-Bipyridine ,Inorganic Chemistry ,chemistry.chemical_compound ,Crystallography ,Bipyridine ,chemistry ,Computational chemistry ,Pyridine ,Non-covalent interactions ,Pi interaction ,Carboxylate ,Lone pair - Abstract
A Cu-II complex of protonated 4,4'-bipyridine (Hbyp) and 2-picolinate (pic), [Cu-2(pic)(3)(Hbyp)(H2O)(ClO4)(2)], has been synthesised and characterised by single-crystal X-ray analysis. The structure consists of two copper atoms that have different environments, bridged by a carboxylate group. The equatorial plane is formed by the two bidentate picolinate groups in one Cu-II, and one picolinate, one monodentate 4,4'-bipyridyl ligand and a water molecule in the other. Each copper atom is also weakly bonded to a perchlorate anion in an axial position. One of the coordinated perchlorate groups displays anion-pi interaction with the coordinated pyridine ring. The noncoordinated carboxylate oxygen is involved in lone-pair (l.p.)-pi interaction with the protonated pyridine ring. In addition there are pi-pi and H-bonding interactions in the structure. Bader's theory of "atoms in molecules" (AIM) is used to characterise the anion-pi and l.p.-pi interactions observed in the solid state. A high-level ab initio study (RI-MP2/aug-cc-pVTZ level of theory) has been performed to analyse the anion-pi binding affinity of the pyridine ring when it is coordinated to a transition metal and also when the other pyridine ring of the 4,4'-bipyridine moiety is protonated. Theoretical investigations support the experimental findings of an intricate network of intermolecular interactions, which is characterised in the studied complex, and also indicate that protonation as well as coordination to the transition metal have important roles in influencing the pi-binding properties of the aromatic ring. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
- Published
- 2009
50. Theoretical ab initio study of the interplay between hydrogen bonding, cation–π and π–π interactions
- Author
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Daniel Escudero, Antonio Frontera, David Quiñonero, Carolina Estarellas, and Pere M. Deyà
- Subjects
chemistry.chemical_classification ,Chemical physics ,Hydrogen bond ,Chemistry ,Computational chemistry ,Ab initio quantum chemistry methods ,Cation π ,Ab initio ,Stacking ,Non-covalent interactions ,Aromaticity ,Physical and Theoretical Chemistry ,Polarization (electrochemistry) - Abstract
The interplay among three important non-covalent interactions involving aromatic rings is studied by means of ab initio calculations (RI-MP2/aug-cc-pVTZ//RI-MP2/aug-cc-pVDZ, and RI-MP2/CBS levels of theory). They demonstrate that synergetic effects are present in complexes where hydrogen bonding interactions, cation–π, and π–π interactions coexist. These synergetic effects have been studied using the genuine non-additivity energies and the molecular interaction potential with polarization partition scheme.
- Published
- 2009
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