دورية أكاديمية
Linear and nonlinear optical properties of a quadrupolar carbo-benzene and its benzenic parent: The carbo-merization effect
| العنوان: | Linear and nonlinear optical properties of a quadrupolar carbo-benzene and its benzenic parent: The carbo-merization effect |
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| المؤلفون: | Barba-Barba, Rodrigo, Chammam, Marwa, Ramos-Ortiz, Gabriel, Listunov, Dymytrii, Velusamy, Jayaramakrishnan, Rodriguez, Mario, Carriles, Ramon, Silva, Carlos, Guyard-Duhayon, Carine, Kauffmann, Brice, Maraval, Valérie, Chauvin, Rémi |
| المساهمون: | Centro de Investigaciones en Optica (CIO), Consejo Nacional de Ciencia y Tecnología Mexico (CONACYT), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Georgia Institute of Technology Atlanta, School of Chemistry and Biochemistry Atlanta, School of Physics Atlanta, Institut Européen de Chimie et Biologie (IECB), Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), ECOS-NORD project (M16P02 and 291434), French Mexican International Laboratory LIA-LCMMC with financial / CNRS - CONACYT, Centre National de la Recherche Scientifique (CNRS), National Science Foundation (DMR-1729737) |
| المصدر: | ISSN: 0143-7208 ; Dyes and Pigments ; https://hal.science/hal-03202845Test ; Dyes and Pigments, 2021, 188, pp.109133. ⟨10.1016/j.dyepig.2021.109133⟩. |
| بيانات النشر: | HAL CCSD Elsevier |
| سنة النشر: | 2021 |
| المجموعة: | Université Toulouse III - Paul Sabatier: HAL-UPS |
| مصطلحات موضوعية: | Carbo-benzenes, Macrocycles, Two-photon absorption, π-conjugation, [CHIM.COOR]Chemical Sciences/Coordination chemistry |
| الوصف: | International audience ; Herein, the optical properties of thiophene-functionalized quadrupolar carbo-benzenes and a benzenic parent, of generic structure Th–Ctriple bondC–[core]–Ctriple bondC–Th, Th = R2C4HS, are comparatively investigated. Beyond the previously unknown dioctylthienylethynylbenzene (core = p-C6H4, R = nOct), two bis-dialkylthienylethynyl-carbo-benzenes (core = C18Ph4, R = nOct, nBu) are envisaged for the unique "carbo-aromatic" character of the C18 macrocycle. The three targets were synthesized from the corresponding ethynylthiophenes in 47, 20 and 10% yield, respectively, then characterized by classical methods such as NMR spectroscopy, and X-ray crystallography for one of the carbo-benzenes. Regarding linear and nonlinear optical properties, our results show that the carbo-merization induces a significant shift to lower energies of the one-photon electronic excitations accompanied by an 8-fold increase of the molar extinction coefficient compared to the parent molecule. Intriguingly, these excitations lead to a broad band of photoluminescence comprising decay transitions of the type S1 → S0 but also of the type S2 → S0. This phenomenon of emission from higher excited states, which is contrary to Kasha's rule, is assigned to - or revealed by - a reduction of the internal conversion efficiency between S2 and S1. Two-photon induced transitions are also enhanced, the two-photon absorption cross-section (σ2PA) being in average five times larger for the carbo-benzenes than for their benzene parent in the wavelength range 650–950 nm, with a maximum of σ2PA = 1430 GM (1 GM = 10−50 cm4 s/photon). Beyond a moderate nonlinearity, this comparative study provides quantitative insights about the way carbo-merization or insertion of a π-conjugated macrocycle between chromophoric functions (here thiophene rings) can tune optical properties of organic molecules. The optical properties of the bis-dialkylthienylethynyl-carbo-benzenes are also discussed in regard of recent reports on organic chromophores based ... |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| العلاقة: | hal-03202845; https://hal.science/hal-03202845Test; https://hal.science/hal-03202845/documentTest; https://hal.science/hal-03202845/file/S0143720821000012.pdfTest; PII: S0143-7208(21)00001-2 |
| DOI: | 10.1016/j.dyepig.2021.109133 |
| الإتاحة: | https://doi.org/10.1016/j.dyepig.2021.109133Test https://hal.science/hal-03202845Test https://hal.science/hal-03202845/documentTest https://hal.science/hal-03202845/file/S0143720821000012.pdfTest |
| حقوق: | http://creativecommons.org/licenses/by-ncTest/ ; info:eu-repo/semantics/OpenAccess |
| رقم الانضمام: | edsbas.7DB8CEDB |
| قاعدة البيانات: | BASE |
| DOI: | 10.1016/j.dyepig.2021.109133 |
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