Chemical Sensors (Modelling the Photophysics of Cation Detection by Organic Dyes)

La présence croissante de diverses substances dans notre environnement, conséquencedes activités anthropiques de ces dernières décennies, a entraîné un besoingrandissant et urgent de nouveaux matériaux et dispositifs dans la quête de senseurschimiques efficaces et fiables. D'énormes progrès technologiques ont permis de mettreà disposition toute une gamme d'outils techniques pour leur développement, enprenant en compte les exigences à respecter en terme de sélectivité ou de rapidité deréponse, entre autres. Dans ce contexte, les méthodes de chimie quantique permettentune compréhension fondamentale des processus en jeu dans la détection des espèceschimiques, et par extension, l'élaboration de manière rationnelle de nouveauxmatériaux sensibles. Certaines molécules organiques pouvant être largementfonctionnalisées, elles constituent un point de départ idéal en raison des importantesmodulations possibles de leurs propriétés par des modifications structuralesappropriées.Cette étude vise à développer de manière rationnelle des chromoionophores pour lacomplexation de cations par une approche combinant méthodes de chimiecomputationnelles et caractérisation par spectroscopie optique. Deux pointsprincipaux ont été traités à l'aide de la Théorie de la Fonctionnelle de la Densité(DFT) et son extension dépendante du temps (TD-DFT): d'une part les relationsstructure moléculaire-propriétés optiques de chromophores, d'autre part le phénomènede complexation. En particulier, la détection de l'ion Zn2+, démontrée de manièrethéorique et expérimentale, est finalement réalisée après intégration du senseurmoléculaire dans un dispositif à fibre optique.The increasing presence of various substances in our environment has brought abouta growing need for rapid emergence of new materials and devices in the quest forefficient and reliable chemical sensors. Massive technological progress have madeavailable an extensive range of technical tools to serve their development, accountingfor the requirements to be fulfilled (selectivity, quick response..). In this context,quantum chemistry methods provide a fundamental understanding of the processes atstake in the detection of chemical species and allow for rational design of sensingmaterials. Certain organic molecules can be extensively functionalised and thusconstitute an evident starting point owing to the tunability of their propertiesprovided by appropriate choice of structural modifications. The versatility of somechromophores associated to the selectivity offered by receptor units constitute theresearch playground for the development of ever better chemosensors.The present research aims at the rational development of chromoionophores for thecomplexation of cations, combining computational chemistry methods with basicspectroscopic characterisation. Using Density Functional Theory (DFT) and its timedependentextension (TD-DFT), two main aspects were treated, namely therelationship between molecular structure and optical properties of organicchromophores featuring valuable characteristics, and the complexation phenomenon.Photophysics of Zn2+ ion detection were more specifically studied, and recognitionwas demonstrated with both quantum-chemical calculations and experiments,accounting for the future integration of the chemical sensor in an optical fibre device.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF

Reversible spin-optical interface in luminescent organic radicals.

peer reviewedMolecules present a versatile platform for quantum information science1,2 and are candidates for sensing and computation applications3,4. Robust spin-optical interfaces are key to harnessing the quantum resources of materials5. To date, carbon-based candidates have been non-luminescent6,7, which prevents optical readout via emission. Here we report organic molecules showing both efficient luminescence and near-unity generation yield of excited states with spin multiplicity S > 1. This was achieved by designing an energy resonance between emissive doublet and triplet levels, here on covalently coupled tris(2,4,6-trichlorophenyl) methyl-carbazole radicals and anthracene. We observed that the doublet photoexcitation delocalized onto the linked acene within a few picoseconds and subsequently evolved to a pure high-spin state (quartet for monoradical, quintet for biradical) of mixed radical-triplet character near 1.8 eV. These high-spin states are coherently addressable with microwaves even at 295 K, with optical readout enabled by reverse intersystem crossing to emissive states. Furthermore, for the biradical, on return to the ground state the previously uncorrelated radical spins either side of the anthracene shows strong spin correlation. Our approach simultaneously supports a high efficiency of initialization, spin manipulations and light-based readout at room temperature. The integration of luminescence and high-spin states creates an organic materials platform for emerging quantum technologies

UV-vis Spectroscopy of the Coupling Products of the Palladium of the Palladium-Catalyzed C-H arylation of the BODIPY Core

peer reviewe

N-Type Solution-Processed Tin versus Silicon Phthalocyanines: A Comparison of Performance in Organic Thin-Film Transistors and in Organic Photovoltaics

Tin(IV) phthalocyanines (SnPcs) are promising candidates for low-cost organic electronic devices, and have been employed in organic photovoltaics (OPVs) and organic thin-film transistors (OTFTs). However, they remain relatively understudied compared to their silicon phthalocyanine (SiPc) analogues. Previously, we reported the first solution-processed SnPc semiconductors for OTFTs and OPVs; however, the performances of these derivatives were unexpected. Herein to further study the behavior of these derivatives in OPVs and OTFTs, we report the synthesis along with optical and thermal characterization of seven axially substituted (OR)2-SnPcs, five of which were synthesized for the first time. Density functional theory (DFT) was used to predict charge-carrier mobilities for our materials in their crystal state. The application of these SnPcs as ternary additives in poly(3-hexylthiophene) (P3HT)/phenyl-C61-butyric acid methyl ester (PC61BM) OPVs and as semiconductors in solution-processed n-type OTFTs was also investigated. When employed as ternary additives in OPVs, all (OR)2-SnPcs decreased the power conversion efficiency, open-circuit voltage, short-circuit current, and fill factor. However, in OTFTs, four of the seven materials exhibited greater electron field-effect mobility with similar threshold voltages compared to their previously studied SiPc analogues. Among these SnPcs, bis(triisobutylsilyl oxide) SnPc displayed the greatest electron field-effect mobility of 0.014 cm2 V-1 s-1, with a threshold voltage of 31.4 V when incorporated into OTFTs. This difference in electrical performance between OTFT and OPV devices was attributed to the low photostability of SnPcs

Thin-Film Engineering of Solution-Processable n-Type Silicon Phthalocyanines for Organic Thin-Film Transistors

Metal and metalloid phthalocyanines are an abundant and established class of materials widely used in the dye and pigment industry as well as in commercial photoreceptors. Silicon phthalocyanines (SiPcs) are among the highest-performing n-type semiconductor materials in this family when used in organic thin-film transistors (OTFTs) as their performance and solid-state arrangement are often increased through axial substitution. Herein, we study eight axially substituted SiPcs and their integration into solution-processed n-type OTFTs. Electrical characterization of the OTFTs, combined with atomic force microscopy (AFM), determined that the length of the alkyl chain affects device performance and thin-film morphology. The effects of high-temperature annealing and spin coating time on film formation, two key processing steps for fabrication of OTFTs, were investigated by grazing-incidence wide-angle X-ray scattering (GIWAXS) and X-ray diffraction (XRD) to elucidate the relationship between thin-film microstructure and device performance. Thermal annealing was shown to change both film crystallinity and SiPc molecular orientation relative to the substrate surface. Spin time affected film crystallinity, morphology, and interplanar d-spacing, thus ultimately modifying device performance. Of the eight materials studied, bis(tri-n-butylsilyl oxide) SiPc exhibited the greatest electron field-effect mobility (0.028 cm2 V-1 s-1, a threshold voltage of 17.6 V) of all reported solution-processed SiPc derivatives

Silicon phthalocyanines for N-type organic thin-film transistors: Development of structure 12property relationships

Silicon phthalocyanines (SiPcs) have shown great potential as n-type or ambipolar organic semiconductors in organic thin-film transistors (OTFTs) and organic photovoltaics. Although properly designed SiPcs rival current state-of-the-art n-type organic semiconducting materials, relatively few structure 12property relationships have been established to determine the impact of axial substituents on OTFT performance, hindering the intelligent design of the next generation of SiPcs. To address this omission, we have developed structure 12property relationships for vapor-deposited SiPcs with phenoxy axial substituents. In addition to thorough electrical characterization of bottom-gate top-contact OTFTs, we extensively investigated SiPc thin films using X-ray diffraction, atomic force microscopy (AFM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and density functional theory (DFT) modeling. OTFT performance, including relative electron mobility (\u3bce) of materials, was in general agreement with values obtained through DFT modeling including reorganization energy. Another significant trend observed from device performance was that increasing the electron-withdrawing character of the axial pendant groups led to a reduction in threshold voltage (VT) from 47.9 to 21.1 V. This was corroborated by DFT modeling, which predicted that VT decreases with the square of the dipole induced at the interface between the SiPc pendant and substrate. Discrepancies between modeling predictions and experimental results can be explained through analysis of thin-film morphology and orientation by AFM and GIWAXS. Our results demonstrate that a combination of DFT modeling to select prospective candidate materials, combined with appropriate processing conditions to deposit molecules with a favorable thin-film morphology in an \u201cedge-on\u201d orientation relative to the substrate, yields high-performance n-type SiPc-based OTFTs