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Yellow, green, and blue plasmonic nanofluids were produced without wet chemistry by direct deposition of Ag, Cu, and simultaneous co-deposition of Ag + Cu nanoparticles from sputter-based gas aggregation cluster sources in liquid polyethylene glycol.

Organic semiconductors combine flexible tailoring of their optoelectronic properties by synthetic means with strong light-matter coupling, which is advantageous for organic electronic device applications. Although spatially selective deposition has been demonstrated, lateral patterning of organic films with simultaneous control of molecular and crystalline orientation is lacking as traditional lithography is not applicable. Here, a new patterning approach based on surface-localized F-centers (halide vacancies) generated by electron irradiation of alkali halides is presented, which allows structural control of molecular adlayers. Combining optical and atomic force microscopy, X-ray diffraction, and density functional theory (DFT) calculations, it is shown that dinaphthothienothiophene (DNTT) molecules adopt an upright orientation on pristine KCl surfaces, while the F-centers stabilize a recumbent orientation, and that these orientations are maintained in thicker films. This specific nucleation results also in different crystallographic morphologies, namely, densely packed islands and jagged fibers, each epitaxially aligned on the KCl surface. Spatially selective surface irradiation can also be used to create patterns of F-centers and thus laterally patterned DNTT films, which can be further transferred to any (including elastomer) substrate due to the water solubility of the alkali halide growth templates.

Three new tetraphenylethene (TPE) push-pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2+2] cycloaddition - retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) as electron-deficient alkene. Only the starting TPE-alkyne displayed a significant AIE behavior, whereas for TPE-TCNE,a faint effect was observed and for TPE-TCNQ and TPE-F4-TCNQ, no fluorescence was observed in any conditions. The main ICT bands that dominate the UV-Visible absorption spectra underwent a pronounced red-shift beyond the near-infrared (NIR) region for TPE-F4-TCNQ. Based on TD-DFT calculations, it was shown that the ICT character shown by the compounds exclusively originated from the clicked moieties independently of the nature of the central molecular platform. Photothermal (PT) studies conducted on both TPE-TCNQ and TPE-F4-TCNQ in the solid state revealed excellent properties, especially for TPE-F4-TCNQ. These results indicated that CA-RE reaction of TCNQ or F4-TCNQ with donor-substituted are promising candidates for PT applications.

The developments made towards increasingly photoactive copper(I) complexes has led to their use in many applications involving light, in particular light emission or photocatalytic activities. Herein, we describe an unprecedented in-depth study of the photophysical properties of two of the most used copper(I) photosensitizers, [Cu(bcp)(Xantphos)]+ and [Cu(bcp)(DPEphos)]+ (bcp = bathocuproine, Xantphos = 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene, DPEphos = Bis[(2-diphenylphosphino)phenyl]ether). This study combines traditional spectroscopic techniques with state-of-the-art femtosecond time-resolved transient absorption and fluorescence up-conversion spectroscopy and is further supported by quantum-chemical calculations. This combined analysis hints at the presence of a low-lying ligand-centered dark triplet state which plays a crucial role by acting as a reservoir for the excited hetereloptic copper(I) complexes.

Synthesis, polymorph investigation, crystallographic study, and fabrication of OFETs in solution-processed thin films of C7-BTBT-C7.

This study is focused on the Y6 electron acceptor to assess the impact of elongating the inner side chain from 8 to 12 carbon atoms by combining DFT calculations, UV-visible spectroscopy, atomic force microscopy analysis and device characterization.

International audience; A number of factors contribute to orbital energy alignment with respect to the Fermi level in molecular tunnel junctions. Here, we report a combined experimental and theoretical effort to quantify the effect of metal image potentials on the highest occupied molecular orbital to Fermi level offset, ε(h), for molecular junctions based on self-assembled monolayers (SAMs) of oligophenylene ethynylene dithiols (OPX) on Au. Our experimental approach involves the use of both transport and photoelectron spectroscopy to extract the offsets, ε(h)(trans) and ε(h)(UPS), respectively. We take the difference in these quantities to be the image potential energy eV(image). In the theoretical approach, we use density functional theory (DFT) to calculate directly eV(image) between positive charge on an OPX molecule and the negative image charge in the Au. Both approaches yield eV(image) ∼ -0.1 eV per metal contact, meaning that the total image potential energy is ∼-0.2 eV for an assembled junction with two Au contacts. Thus, we find that the total image potential energy is 25-30% of the total offset ε(h), which means that image charge effects are significant in OPX junctions. Our methods should be generally applicable to understanding image charge effects as a function of molecular size, for example, in a variety of SAM-based junctions.

International audience; To date, all efficient host materials reported for phosphorescent OLEDs (PhOLEDs) are constructed with heteroatoms, which have a crucial role in the device performance. However, it has been shown in recent years that the heteroatoms not only increase the design complexity but can also be involved in the instability of the PhOLED, which is nowadays the most important obstacle to overcome. Herein, we design pure aromatic hydrocarbon materials (PHC) as very efficient hosts in high-performance white and blue PhOLEDs. With EQE of 27.7 %, the PHC-based white PhOLEDs display similar efficiency as the best reported with heteroatom-based hosts. Incorporated as a host in a blue PhOLED, which are still the weakest links of the technology, a very high EQE of 25.6 % is reached, overpassing, for the first time, the barrier of 25 % for a PHC and FIrpic blue emitter. These performance show that the PHC strategy represents an effective alternative for the future development of the OLED industry.

Peptoids are peptide regioisomers with attractive structural tunability in terms of sequence and three-dimensional arrangement. Peptoids are foreseen to have a great potential for many diverse applications, including their utilization as a chiral stationary phase in chromatography. To achieve chiral recognition, a chiral side chain is required to allow specific interactions with a given enantiomer from a racemic mixture. One of the most studied chiral stationary phases, built with (S)-N-1-phenylethyl (Nspe) units, was shown to be successful in resolving racemic mixtures of binaphthyl derivatives. However, there is currently no description at the atomic scale of the factors favoring its enantioselectivity. Here, we take advantage of steered molecular dynamics simulations to mimic the elution process at the atomic scale and present evidence that the predominantly right-handed helical conformation of Nspe peptoids and their ability to form stronger hydrogen bonds with the (S) enantiomer are responsible for the chiral recognition of the popular chiral probe 2,2′-bihydroxy-1,1′-binaphthyl.

We study by scanning thermal microscopy the nanoscale thermal conductance of films (40-400 nm thick) of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8). We demonstrate that the out-of-plane thermal conductivity is significant along the interlayer direction, larger for BTBT (0.63 ± 0.12 W m-1 K-1) compared to C8-BTBT-C8 (0.25 ± 0.13 W m-1 K-1). These results are supported by molecular dynamics calculations (approach to equilibrium molecular dynamics method) performed on the corresponding molecular crystals. The calculations point to significant thermal conductivity (3D-like) values along the 3 crystalline directions, with anisotropy factors between the crystalline directions below 1.8 for BTBT and below 2.8 for C8-BTBT-C8, in deep contrast with the charge transport properties featuring a two-dimensional character for these materials. In agreement with the experiments, the calculations yield larger values in BTBT compared to C8-BTBT-C8 (0.6-1.3 W m-1 K-1versus 0.3-0.7 W m-1 K-1, respectively). The weak thickness dependence of the nanoscale thermal resistance is in agreement with a simple analytical model. This journal is, M. G., D. G., S. L. and D. V. thank the ANR for financial support (ANR-16-CE05-0029). Y. G. is thankful to the Belgian National Fund for Scientific Research (FNRS) for financial support through research projects BTBT (# 2.4565.11), Phasetrans (# T.0058.14), Pi-Fast (# T.0072.18), 2D to 3D (# 30489208), and DIFFRA (# U.G001.19). Financial supports from the French Community of Belgian (ARC # 20061) is also acknowledged. G. S. acknowledges postdoctoral fellowship support from the FNRS. The work in the Laboratory for Chemistry of Novel Materials was supported by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under grant # 2.5020.11. J.C. and A.V. are FNRS research fellows.

We report on the growth of metal- and metal-oxide based nanoparticles (NPs) in heated polyol solutions. For this purpose, NPs are produced by the sputtering of a silver, gold, or a copper target to produce either silver, gold, or copper oxide NPs in pentaerythritol ethoxylate (PEEL) which has been annealed up to 200 °C. The objective of the annealing step is the fine modulation of their size. Thus, the evolution of the NP size and shape after thermal annealing is explained according to collision/coalescence kinetics and the affinity between the metal-/metal-oxide and PEEL molecule. Moreover, highlights of few phenomena arising from the annealing step are described such as (i) the reduction of copper oxide into copper by the polyol process and (ii) the effective formation of carbon dots after annealing at 200 °C.

Four trinuclear ruthenium(II) polypyridyl complexes were synthesized, and a detailed investigation of their excited-state properties was performed. The tritopic sexi-pyridine bridging ligands were obtained via para or meta substitution of a central 2,2′-bipyridine fragment. A para connection between the 2,2′-bipyridine chelating moieties of the bridging ligand led to a red-shifted MLCT absorption band in the visible part of the spectra, whereas the meta connection induced a broadening of the LC transitions in the UV region. A convergent energy transfer from the two peripheral metal centers to the central Ru(II) moiety was observed for all trinuclear complexes. These complexes were in thermal equilibrium with an upper-lying 3MLCT excited state over the investigated range of temperatures. For all complexes, deactivation via the 3MC excited state was absent at room temperature. Importantly, the connection in the para position for both central and peripheral 2,2′-bipyridines of the bridging ligand resulted in a trinuclear complex (Tpp) that absorbed more visible light, had a longer-lived excited state, and had a higher photoluminescence quantum yield than the parent [Ru(bpy)3]2+, despite its red-shifted photoluminescence. This behavior was attributed to the presence of a highly delocalized excited state for Tpp.

N-doped TiO2 materials have recently attracted a considerable amount of interest due to their enhanced photoelectrochemical properties compared to pristine TiO2. However, this improvement is still ...

Stacked two-dimensional (2D) heterostructures are evolving as the “next-generation” optoelectronic materials because of the possibility of designing atomically thin devices with outstanding charact...

Peptoids are attractive substitutes for peptides in several research areas, especially when they adopt a helical structure. The chain-size evolution of the secondary structure of the widely studied (S)-N-1-phenylethyl peptoids is here analyzed by means of the ion mobility mass spectrometry technique increasingly used as a powerful analytical tool and is further supported by theoretical modeling. We conclude that the helical shape of the peptoids prevailing in solution is lost in the gas phase by the need to screen the positive charge borne by the peptoid even though the collisional cross sections are close to the values expected for helical systems. We further illustrate that trend line analyses predicting molecular shapes from fits of the size evolution of cross sections can be very misleading since they critically depend on the range of polymerization degrees under study.

The rise of van der Waals hetero-structures based on transition metal dichalcogenides (TMDs) opens the door to a new generation of optoelectronic devices. A key factor controlling the operation and performance of such devices is the relative alignment of the band edges of the components. The electronic properties of the layers can be further modulated by chemical doping, typically leading to the introduction of gap states. However, it is not clear whether the impact of doping in a given layer is preserved when building vertical stacks incorporating it. This has motivated the present study aiming at shedding light by means of first-principles calculations on the electronic properties of heterogeneous bilayers containing one doped layer. Doping has been achieved based on the experimental literature by inserting the dopants by substitution in the 2D layer, by covalently attaching adatoms or functional groups on the surface, or by physisorbing electroactive molecules. Interestingly, very different scenarios can be encountered depending on the two materials present and the nature of doping. The impact of doping is preserved when the trap levels associated with the dopants lie in the bandgap of the bilayer. On the other hand, the pristine neutral layer can get doped to an extent depending on how its electrons can fill the trap levels associated with the other component. Altogether, the present theoretical work demonstrates that the properties of the bilayers are not simply defined by additive rules of the components.

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An increasing number of studies take advantage of ion mobility spectrometry (IMS) coupled to mass spectrometry (IMS-MS) to investigate the spatial structure of gaseous ions. Synthetic polymers occupy a unique place in the field of IMS-MS. Indeed, due to their intrinsic dispersity, they offer a broad range of homologous ions with different lengths. To help rationalize experimental data, various theoretical approaches have been described. First, the study of trend lines is proposed to derive physicochemical and structural parameters. However, the evaluation of data fitting reflects the overall behavior of the ions without reflecting specific information on their conformation. Atomistic simulations constitute another approach that provide accurate information about the ion shape. The overall scope of this review is dedicated to the synergy between IMS-MS and theoretical approaches, including computational chemistry, demonstrating the essential role they play to fully understand/interpret IMS-MS data.

Folding and unfolding processes are key aspects that should be mastered for the design of foldamer molecules for targeted applications. In contrast to the solution phase, in vacuo conditions represent a well-defined environment to analyze the intramolecular interactions that largely control the folding/unfolding dynamics. Ion mobility mass spectrometry coupled to theoretical modeling represents an efficient method to decipher the spatial structures of gaseous ions, including foldamers. However, charge solvation typically compacts the ion structure in the absence of strong stabilizing secondary interactions. This is the case in peptoids that are synthetic peptide regioisomers whose side chains are connected to the nitrogen atoms of the backbone instead of α-carbon as in peptides, thus implying the absence of H-bonds among the core units of the backbone. A recent work indeed reported that helical peptoids based on Nspe units formed in solution do not retain their secondary structure when transferred to the gas phase upon electrospray ionization (ESI). In this context, we demonstrate here that the helical structure of peptoids bearing (S)-N-(1-carboxy-2-phenylethyl) bulky side chains (Nscp) is largely preserved in the gas phase by the creation of a hydrogen bond network, induced by the presence of carboxylic moieties, that compensates for the charge solvation process.

Mass spectrometric techniques and more particularly collision-induced dissociation (CID) experiments represent a powerful method for the determination of the primary sequence of (bio)molecules. However, the knowledge of the ion fragmentation patterns say the dissociation reaction mechanisms is a prerequisite to reconstitute the sequence based on fragment ions. Previous papers proposed that protonated peptoids dissociate following an oxazolone-ring mechanism starting from the O-protonation species and leading to high mass Y sequence ions. Here we revisit this backbone cleavage mechanism by performing CID and ion mobility experiments, together with computational chemistry, on tailor-made peptoids. We demonstrated that the B/Y cleavages of collisionally activated O-protonated peptoids must involve the amide nitrogen protonated structures as the dissociating species, mimicking the CID behavior of protonated peptides. Upon the nucleophilic attack of the oxygen atom of the N-terminal adjacent carbonyl group on the carbonyl carbon atom of the protonated amide, the peptoid ions directly dissociate to form an ion-neutral complex associating an oxazolone ion to the neutral truncated peptoid residue. Dissociation of the ion/neutral complex predominantly produces Y ions due to the high proton affinity of the secondary amide function characteristic of truncated peptoids. Whereas the production of Yx ions from acetylated peptoids also involves the B/Y pathway, the observation of abundant Yx ions from non-acetylated peptoid ions is shown in the present study to arise from an A1-Yx mechanism. The consecutive and competitive characters of the A1-Yx and the B/Y mechanisms are also investigated by drift time-aligned CID experiments.

International audience; We report a novel class of star-shaped multiazobenzene photoswitches comprising individual photochromes connected to a central trisubstituted 1,3,5-benzene core. The unique design of such C3-symmetric molecules, consisting of conformationally rigid and pseudoplanar scaffolds, made it possible to explore the role of electronic decoupling in the isomerization of the individual azobenzene units. The design of our tris-, bis-, and mono(azobenzene) compounds limits the π-conjugation between the switches belonging to the same molecule, thus enabling the efficient and independent isomerization of each photochrome. An in-depth experimental insight by making use of different complementary techniques such as UV–vis absorption spectroscopy, high performance liquid chromatography, and advanced mass spectrometry methods as ion mobility revealed an almost complete absence of electronic delocalization. Such evidence was further supported by both experimental (electrochemistry, kinetical analysis) and theoretical (DFT calculations) analyses. The electronic decoupling provided by this molecular design guarantees a remarkably efficient photoswitching of all azobenzenes, as evidenced by their photoisomerization quantum yields, as well as by the Z-rich UV photostationary states. Ion mobility mass spectrometry was exploited for the first time to study multiphotochromic compounds revealing the occurrence of a large molecular shape change in such rigid star-shaped azobenzene derivatives. In view of their high structural rigidity and efficient isomerization, our multiazobenzene photoswitches can be used as key components for the fabrication of complex stimuli-responsive porous materials.

Despite offering robust mechanical properties, polymer networks suffer from a lack of recyclability, reshaping, and healability. Designing stiff and remendable polymer networks that can repair under mild conditions remains a challenge to extend their field of applications. Herein, we describe a simple approach to design a nonisocyanate-based polyurethane network featuring multiresponsiveness (to humidity and temperature) and outstanding healing properties, as obtained by combining iminoboronate and boroxine chemistry. In spite of the presence of abundant dynamic bonds, the network has a high stiffness (Young's modulus of 551 MPa) and tensile strength (11 MPa). C?N iminoboronate and B-O boroxine exchange reactions at high temperature enable efficient network recycling over multiple cycles without compromising its properties. Owing to these features, 3D objects could be designed and printed. The present approach provides excellent sustainable and high-performance substitution to conventional polyurethane networks requiring the use of toxic isocyanates., SCOPUS: ar.j, info:eu-repo/semantics/published

Peptoids constitute an emergent class of synthetic biocompatible macromolecules that are best described as polymers of N-substituted glycines. Peptides and peptoids are regioisomers with the side chains appended in peptoids to the nitrogen atoms rather than to the α-carbon atoms as in peptides. Peptide sequencing now takes great advantage of collision-induced dissociation experiments, based on the elucidation of the decomposition pathways of protonated peptides. In contrast, data on peptoid ion decompositions are to date scarcely present in the literature. Upon CID, protonated peptoids were recently shown to mostly dissociate by cleavages at the backbone amide bonds yielding B- and Y-fragment ions. In addition, the loss of the side-chain group and/or the formation of the side-chain fragment ion are common reactions for peptoids containing protonated N-α-aromatic side chain. In the present paper, we submitted protonated tailor-made peptoids to (energy-resolved) collision-induced dissociation experiments to investigate the side-chain loss reaction mechanisms. We also used orthogonal methods, such as quantum chemistry, ion mobility spectrometry and infrared photodissociation spectroscopy to establish the structures of the fragment ions. We ended up with different mechanistic scenarios consistent with the nature of the fragment ions and the kinetic energy dependence of decomposition reactions. Our mechanistic proposals associate the proton mobile model, proton bound dimer intermediacy and concerted rearrangement reactions.

Recent studies point to an additional stability of metal-complexed functionalized hydrocarbon chains. This additional stabilization is suggested to arise from a bidentate complexation of the metal cation with both the functional group and aliphatic chain, leading to more folded structures. In the present work, this issue is verified for silver complexed alkylamines by tandem mass spectrometry and ion mobility experiments combined with quantum-chemical calculations. Upon increasing the length of the hydrocarbon chains, the alkylamine/silver complexes undergo a structural transition to reach a folded structure in which the silver cation interacts with both the amine group and hydrogen atoms located at the chain end. This folding is further examined by monitoring the loss of AgH upon collision-induced dissociation experiments performed on alkylamines with different chain lengths. Ion mobility experiments performed on the fragment ions indicate that the removal of the silver cation induces the unfolding of the chain.

International audience

We report the formation of self-assembled monolayers of a molecular photoswitch (azobenzene-bithiophene derivative, AzBT) on cobalt via a thiol covalent bond. We study the electrical properties of the molecular junctions formed with the tip of a conductive atomic force microscope under ultra-high vacuum. The statistical analysis of the current-voltage curves shows two distinct states of the molecule conductance, suggesting the coexistence of both the trans and cis azobenzene isomers on the surface. The cis isomer population (trans isomer) increases (decreases) upon UV light irradiation. The situation is reversed under blue light irradiation. The experiments are confronted to first-principle calculations performed on the molecular junctions with the Non-Equilibrium Green's Function formalism combined with Density Functional Theory (NEGF/DFT). The theoretical results consider two different molecular orientations for each isomer. Whereas the orientation does not affect the conductance of the trans isomer, it significantly modulates the conductance of the cis isomer and the resulting conductance ON/OFF ratio of the molecular junction. This helps identifying the molecular orientation at the origin of the observed current differences between the trans and cis forms. The ON state is associated to the trans isomer irrespective of its orientation in the junction, while the OFF state is identified as a cis isomer with its azobenzene moiety folded upward with respect to the bithiophene core. The experimental and calculated ON/OFF conductance ratios have a similar order of magnitude. This conductance ratio seems reasonable to make these Co-AzBT molecular junctions a good test-bed to further explore the relationship between the spin-polarized charge transport, the molecule conformation and the molecule-Co spinterface., Full manuscript and supporting information

Graphdiyne (GDY), which features a highly π-conjugated structure, direct bandgap, and high charge carrier mobility, presents the major requirements for photocatalysis. Up to now, all photocatalytic studies are performed without paying too much attention on the GDY bandgap (1.1 eV at the GW many-body theory level). Such a narrow bandgap is not suitable for the band alignment between GDY and other semiconductors, making it difficult to achieve efficient photogenerated charge carrier separation. Herein, for the first time, it is demonstrated that tuning the electronic bandgap of GDY via H-substitution (H-GDY) promotes interfacial charge separation and improves photocatalytic H evolution. The H-GDY exhibits an increased bandgap energy (≈2.5 eV) and exploitable conduction band minimum and valence band maximum edges. As a representative semiconductor, TiO is hybridized with both H-GDY and GDY to fabricate a heterojunction. Compared to the GDY/TiO, the H-GDY/TiO heterojunction leads to a remarkable enhancement of the photocatalytic H generation by 1.35 times under UV–visible illumination (6200 µmol h g) and four times under visible light (670 µmol h g). Such enhancement is attributed to the suitable band alignment between H-GDY and TiO, which efficiently promotes the photogenerated electron and hole separation, as supported by density functional theory calculations., The work in Mons was supported by the Belgian National Fund for Scientific Research (FRS-FNRS). Computational resources were provided by the Consortium des Équipements de Calcul Intensif (CÉCI) funded by F.R.S.-FNRS under Grant No. 2.5020.11. J.C. is an FNRS research director. ICN2 acknowledges funding from Generalitat de Catalunya 2017 SGR 327 and the Spanish MINECO project ENE2017-85087-C3. ICN2 was supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706) and was funded by the CERCA Programme/Generalitat de Catalunya. Part of the present work was performed in the framework of Universitat Autònoma de Barcelona Materials Science Ph.D. program. X.H. thanks China Scholarship Council for scholarship support (201804910551).

The charge transport of crystalline organic semiconductors is limited by dynamic disorder that tends to localize charges. It is the main hurdle to overcome in order to significantly increase charge carrier mobility. An innovative design that combines a chemical structure based on sulfur rich thienoacene with a solid state herringbone HB packing is proposed and the synthesis, physicochemical characterization, and charge transport properties of two new thienoacenes bearing a central tetrathienyl core fused with two external naphthyl rings naphtho[2,3 b]thieno [2 amp; 8242; amp; 8242; amp; 8242;,3 amp; 8242; amp; 8242; amp; 8242; 4 amp; 8242; amp; 8242;,5 amp; 8242; amp; 8242;]thieno[2 amp; 8243;,3 amp; 8243; 4 amp; 8242;,5 amp; 8242;]thieno[3 amp; 8242;,2 amp; 8242; b]naphtho[2,3 b]thiophene DN4T and naphtho[1,2 b]thieno [2 amp; 8242; amp; 8242; amp; 8242;,3 amp; 8242; amp; 8242; amp; 8242; 4 amp; 8242; amp; 8242;,5 amp; 8242; amp; 8242;]thieno[2 amp; 8242; amp; 8242;,3 amp; 8242; amp; 8242; 4 amp; 8242;,5 amp; 8242;]thieno[3 amp; 8242;,2 amp; 8242; b]naphtho[1,2 b]thiophene are presented. Both compounds crystallize with a HB pattern structure and present transfer integrals ranging from 33 to 99 meV for the former within the HB plane of charge transport. Molecular dynamics simulations point toward an efficient resilience of the transfer integrals to the intermolecular sliding motion commonly responsible for strong variations of the electronic coupling in the crystal. Best device performances are reached with DN4T with hole mobility up to amp; 956; 2.1 cm2 V amp; 8722;1s amp; 8722;1 in polycrystalline organic field effect transistors, showing the effectiveness of the electronic coupling enabled by the new aromatic core. These promising results pave the way to the design of high performing materials based on this new thienoacene, notably through the introduction of alkyl side chains

Control over the energy level alignment in molecular junctions is notoriously difficult, making it challenging to control basic electronic functions such as the direction of rectification. Therefore, alternative approaches to control electronic functions in molecular junctions are needed. This paper describes switching of the direction of rectification by changing the bottom electrode material M = Ag, Au, or Pt in M–S(CH2)11S–BTTF//EGaIn junctions based on self-assembled monolayers incorporating benzotetrathiafulvalene (BTTF) with EGaIn (eutectic alloy of Ga and In) as the top electrode. The stability of the junctions is determined by the choice of the bottom electrode, which, in turn, determines the maximum applied bias window, and the mechanism of rectification is dominated by the energy levels centered on the BTTF units. The energy level alignments of the three junctions are similar because of Fermi level pinning induced by charge transfer at the metal–thiolate interface and by a varying degree of additional charge transfer between BTTF and the metal. Density functional theory calculations show that the amount of electron transfer from M to the lowest unoccupied molecular orbital (LUMO) of BTTF follows the order Ag > Au > Pt. Junctions with Ag electrodes are the least stable and can only withstand an applied bias of ±1.0 V. As a result, no molecular orbitals can fall in the applied bias window, and the junctions do not rectify. The junction stability increases for M = Au, and the highest occupied molecular orbital (HOMO) dominates charge transport at a positive bias resulting in a positive rectification ratio of 83 at ±1.5 V. The junctions are very stable for M = Pt, but now the LUMO dominates charge transport at a negative bias resulting in a negative rectification ratio of 912 at ±2.5 V. Thus, the limitations of Fermi level pinning can be bypassed by a judicious choice of the bottom electrode material, making it possible to access selectively HOMO- or LUMO-based charge transport and, as shown here, associated reversal of rectification., The authors express thanks to the Ministry of Education (MOE) for supporting this research under award nos. MOE2018-T2-1-088 and R-143-000-B30-112. We also acknowledge the Prime Minister’s Office, Singapore, under its Medium Sized Centre program for supporting this research. This work was also funded by ITN iSwitch 642196, the DGI (Spain), projects FANCY (CTQ2016-80030-RA), GENESIS (PID2019-111682RB-I00) and MOTHER (MAT2016-80826- R), the Generalitat de Catalunya (2017-SGR-918), the Instituto de Salud Carlos III, through “Acciones CIBER”, and the Spanish Ministry of Economy and Competitiveness through the “Severo Ochoa” program for Centers of Excellence in R&D (FUNFUTURE; CEX2019-000917-S). The work in Mons was financially supported by the EC through the Marie Curie project ITN iSwitch (GA no. 642196). Computational resources were provided by the Consortium des É quipements de Calcul Intensif (CÉ CI) funded by the Belgian National Fund for Scientific Research (F.R.S.-FNRS) under grant 2.5020.11. J.C. is an FNRS research director.

Fitting the I/V curves of molecular junctions by simple analytical models is often done to extract relevant molecular parameters such as energy level alignment or interfacial electronic coupling to build up useful property-relationships. However, such models can suffer from severe limitations and hence provide unreliable molecular parameters. This is illustrated here by extracting key molecular parameters by fitting computed voltage-dependent transmission spectra and by comparing them to the values obtained by fitting the calculated I/V curves with a typical Lorentzian model used in the literature. Doing so, we observe a large discrepancy between the two sets of values which warns us about the risks of using simple fitting expressions. Interestingly, we demonstrate that the quality of the fit can be improved by imposing the low bias conductance and Seebeck coefficient of the junction to be recovered in the fitting procedure.

We investigate at the theoretical (time-dependent) density functional theory level the influence of the nature of the anchoring group on the electronic and optical properties of oligothiophene dyes when adsorbed on ${\mathrm{Ti}\mathrm{O}}_{2}$ surface. The computed electronic structures point to a strong orbital hybridization between the dye and the substrate in the presence of the carboxylic acid and thiocarboxylic acid group, leading to a pronounced pinning effect of the lowest unoccupied molecular orbital (LUMO) level and faster electron injection. In contrast, phosphonic acid and catechol promote a weak electronic coupling between the two components and hence slower injection times. The simulated absorption spectra demonstrate that carboxylic and thiocarboxylic anchoring groups can induce a large redshift of the lowest optical transition of the dye upon adsorption due to a strong stabilization of the LUMO level triggered by the pinning effect while a small redshift prevails for phosphonic and catechol dyes. When pinning is active, the chain-size evolution of the lowest optical transition is also less sensitive to the conjugation length compared to the free dyes.

Synthetic polymers occupy a unique place in the field of ion mobility mass spectrometry (IMS-MS). Indeed, due to their intrinsic dispersity, they have the asset to offer a broad range of homologous ions with different lengths that can be detected in several charge states. In addition, the gas-phase structure of polymer ions mostly depends on their ability to screen the adducted charges. Several works dealing with linear, cyclic, and star-shaped polymers have already shown that the gas-phase structure of polymer ions heavily relies on the polymer architecture, i.e., the primary structure. In the present work, we move a step further by evaluating whether a relationship exists between the primary and secondary structures of synthetic homo and copolymers. The IMS-MS experiments will be further complemented by MD simulations. To highlight the effectiveness of IMS separation, we selected isomeric homo and copolymers made of lactide (LA) and propiolactone (PL) units. In this way, the mass analysis becomes useless since isomeric comonomer sequences can coexist for any given chain length. An UPLC method was implemented in the workflow to successfully separate all PL-LA comonomer sequences before infusion in the IMS-MS instrument. The analysis of doubly charged copolymers showed that the comonomer sequence has an impact on the IMS response. However, this only holds for copolymer ions with precise sizes and charge states, and this is therefore not a rule of thumb.

The stereoisomerically pure synthesis of a novel heptanuclear Ru(II)–Os(II) antenna bearing multitopic terpyridine ligands is reported. An unambiguous structural characterization was obtained by 1H NMR spectroscopy and ion mobility spectrometry (IMS-MS). The heptanuclear complex exhibits large molar absorption coefficients (77900 M–1 cm–1 at 497 nm) and undergoes unitary, downhill, convergent energy transfer from the peripheral Ru(II) subunits to the central Os(II) that displays photoluminescence with a lifetime (τ = 161 ns) competent for diffusional excited-state electron transfer reactivity in solution.

Low-emissivity glasses rely on multistacked architectures with a thin silver layer sandwiched between oxide layers. The mechanical stability of the silver/oxide interfaces is a critical parameter that must be maximized. Here, we demonstrate by means of quantum-chemical calculations that a low work of adhesion at interfaces can be significantly increased via doping and by introducing vacancies in the oxide layer. For the sake of illustration, we focus on the ZrO2(111)/Ag(111) interface exhibiting a poor adhesion in the pristine state and quantify the impact of introducing n-type dopants or p-type dopants in ZrO2 and vacancies in oxygen atoms (nVO; with n = 1, 2, 4, 8, 10, 16), zirconium atoms (mVZr; with m = 1, 2, 4, 8), or both (nVO + mVZr; with m/n = 1:2, 1:4, 2:2, 2:4). In the case of doping, interfacial electron transfer promotes an increase in the work of adhesion, from initially 0.16 to ∼0.8 J m-2 (n-type) and ∼2.0 J m-2 (p-type) at 10% doping. A similar increase in the work of adhesion is obtained by introducing vacancies, e.g., VO [VZr] in the oxide layer yields a work of adhesion of ∼1.5-2.0 J m-2 at 10% vacancies. An increase is also observed when mixing VO and VZr vacancies in a nonstoichiometric ratio (nVO + mVZr; with 2n ≠ m), while a stoichiometric ratio of VO and VZr has no impact on the interfacial properties.

Stacked two-dimensional (2D) heterostructures are evolving as the "next-generation" optoelectronic materials because of the possibility of designing atomically thin devices with outstanding characteristics. However, most of the existing 2D heterostructures are governed by weak van der Waals interlayer interactions that, as often is the case, exert limited impact on the resulting properties of heterostructures relative to their constituting components. In this work, we investigate the optoelectronic properties of a novel class of 2D MP

Recent advances in molecular dynamics (MD) simulations have made it possible to examine the behavior of large charged droplets that contain analytes such as proteins or polymers, thereby providing insights into electrospray ionization (ESI) mechanisms. In the present study, we use this approach to investigate the release of polylactide (PLA) ions from water/acetonitrile ESI droplets. We found that cationized gaseous PLA ions can be formed via various competing pathways. Some MD runs showed extrusion and subsequent separation of polymer chains from the droplet, as envisioned by the chain ejection model (CEM). On other occasions the PLA chains remained inside the droplets and were released after solvent evaporation to dryness, consistent with the charge residue model (CRM). Following their release from ESI droplets, the nascent gaseous PLA ions were subjected to structural relaxation for several μs in vacuo. The MD conformations generated in this way for various PLA charge states compared favorably to experimental results obtained by ion mobility spectrometry-mass spectrometry (IMS-MS). The structures of all PLA ions evolved during relaxation in the gas phase. However, some macroion species retained features that resembled their nascent structures. For this subset of ions, the IMS-MS response appears to be strongly correlated with the ESI release mechanism (CEM vs. CRM). The former favored extended structures, whereas the latter preferentially generated compact conformers.

The two-dimensional shape information yielded by ion mobility-mass spectrometry (IM-MS), usually reported as collision cross section (CCS), is often correlated to the underlying three-dimensional structures of the ions through computational chemistry. Here, we used theoretical approaches based on molecular mechanics (MM), molecular dynamics (MD), and density functional theory (DFT) to elucidate the structures of sodiated poly(ethoxy phosphate) polymer ions at different degrees of polymerization (DP) for three different charge states (1+, 2+, and 3+) by comparing computational results to experimentally obtained CCS values. From the calculated structures, we extract several key interaction distances which merge in clusters for all screened charge states and DPs, independent of the three-dimensional structures and the polymer ion structural rearrangements. These distances were also used to extract the minimum coordination numbers in poly(ethoxy phosphate) and to describe the preferred coordination geometries. When sodiated and protonated polymer ions are compared, the experimental CCS evolutions differ at small DP values and merge at higher DPs. We investigated in more depth this difference for two selected species, namely, [PEtP

Al-doped ZnO is well known as an alternative Transparent Conductive Oxide (TCO) to Indium Tin Oxide (ITO). Recently, co-doped ZnO with Ti and Al (TAZO) have been explored to improve the conductivity while maintaining moisture durability and opto-electronic properties. In this context, the structural, morphological, and optical properties of TAZO films deposited by reactive magnetron are investigated by experiments and Density Functional Theory (DFT) simulations. The results show that TiO2 units substitute Zn atoms in the ZnO wurtzite structure and, whatever the concentration of Ti, the formation of Al2O3 is taking place. In addition, a three-regime model as a function of Ti content is proposed to explain the evolution of the properties. First, for Ti content 〈 2.2 at%, TiO2 is incorporated by substitution of Zn by TiO2 units in the ZnO network leading to a more oxidized Zn state and a hybridization between Zn4s and Ti3d orbitals. This opens the bandgap and increases the compressive stress of TAZO films. Between 2.2 at% and 7.0 at% of Ti content, cauliflower shape grains appear due to the compressive stress induced by small clusters of TiO2. For Ti content 〉 7.0 at%, amorphous TAZO films are observed and are composed of TiO2, Al2O3 and ZnO.

Highly (Z)-diastereoselective approaches for the synthesis of trifluoromethylated exo-glycals by copper and photoredox catalysis are described. These complementary reactions are applicable to a wide range of methylene exo-glycals generated from the corresponding pyranoses and furanoses and give trifluoromethylated compounds under mild conditions in moderate to good yields. DFT calculations have allowed a rationalization of the observed (Z)-stereoselectivity.

For many applications, as for example tandem dye-sensitized solar cells (DSSCs), the development of transparent p-type semiconductor with good charge transport properties is crucial. In this work, a nitrogen-doped TiO2 material is transformed by ion implantation into an efficient hole transport layer that could reduce the electron-hole recombination processes in the devices. Theoretical calculations allowed to demonstrate that the position of nitrogen species as well as their respective ratio impact the optical and electrical properties of N-doped TiO2 materials. The chemical composition was therefore tuned by the ion implantation parameters, achieving a high transparency in the UV–visible region while generating delocalized states near the top of the valence band that do not act as traps. In terms of electrical properties, beyond the possibility to tune the electrical behavior of TiO2 from n-type to p-type upon nitrogen doping, we succeed to increase the conductivity by a higher electron mobility without change in their density, which is of prime interest for charge transport application.

In the field of polymer characterization, the use of ion mobility mass spectrometry (IMMS) remains mainly devoted to the temporal separation of cationized oligomers according to their charge states, molecular masses and macromolecular architectures in order to probe the presence of different structures. When analyzing multiply charged polymer ions by IMMS, the most striking feature is the observation of breaking points in the evolution of the average collision cross sections with the number of monomer units. Those breaking points are associated to the folding of the polymer chain around the cationizing agents. Here, we scrutinize the shape of the arrival time distribution (ATD) of polylactide ions and associate the broadening as well as the loss of symmetry of the ATD signals to the coexistence of different populations of ions attributed to the transition from opened to folded stable structures. The observation of distinct distributions reveals the absence of folded/extended structure interconversion on the ion mobility time scale (1-10 ms) and then on the lifetime of ions within the mass spectrometer at room temperature. In order to obtain information on the possible interconversion between the different observed populations upon ion activation, we performed IM-IM-MS experiments (tandem ion mobility measurements). To do so, mobility-selected ions were activated by collisions before a second mobility measurement. Interestingly, the conversion by collisional activation from a globular structure into a (partially) extended structure, i.e. the gas phase unfolding of the ions, was not observed in the energetic regime available with the used experimental setup. The absence of folded/extended interconversion, even upon collisional activation, points to the fact that the polylactide ions are 'frozen' in their specific 3D structure during the desolvation/ionization electrospray processes. Copyright © 2017 John Wiley & Sons, Ltd.

Self-healing polymeric materials that can spontaneously repair in a perpetual manner are highly appealing to address safety and restoration issues in different key applications. Usually built from reversible moieties that require to be activated using, for example, temperature, light, or pH changes, most of these self-healing materials rely on energy-demanding processes and/or external interventions to promote self-healing. In this work, we propose to exploit rapid dynamic exchanges between urea-based moieties and moisture as an alternative to promote local and spontaneous healing responses to damage using atmospheric moisture as an external stimulus. Non-hygroscopic urea-based polyurethanes with repetitive moisture-induced healing abilities at different degrees of humidity were thus designed through coupling reactions with non-hygroscopic polypropylene glycol and urea moieties. As supported by density functional theory (DFT) calculations coupled to local FTIR experimental studies, we furthermore established that the healing mechanism is ultimately related to the formation of water-urea clusters. Obviously, this work represents a platform for designing more advanced spontaneous self-healing materials beyond the present study, which hold promise for use in a wide range of technological applications.

There is a growing interest in utilizing the distinctive material properties of organic semiconductors for spintronic applications. Here, we explore the injection of pure spin current from Permalloy into a small molecule system based on dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) at ferromagnetic resonance. The unique tunability of organic materials by molecular design allows us to study the impact of interfacial properties on the spin injection efficiency systematically. We show that both the spin injection efficiency at the interface and the spin diffusion length can be tuned sensitively by the interfacial molecular structure and side chain substitution of the molecule., info:eu-repo/semantics/published

Increasing the crystallinity of thin films in concert with the planarization of the conjugated backbones has long been considered as the key for success in the design of polymer materials with optimized charge transport properties. Recently, this general belief had to be revisited with the emergence of a new class of disordered or even seemingly amorphous donor− acceptor conjugated polymers that exhibit charge mobilities larger than 1 cm2 V−1 s −1 . By combining all-atom molecular dynamics simulations to electronic structure calculations on three representative polymers, we demonstrate that high crystallinity and planar conjugated backbones are not mandatory to reach low-energetic-disorder materials. It is rather the resilience to thermal fluctuations of the torsions along the conjugated backbones within and between structural domains and the bulkiness of the alkyl side chains that control the energy landscape.