Photophysical properties of push-π-pull type chromophores of aryl-substituted bipyridines in different solvents
| Autor: | Lucas F. Bezerra, Elisane Longhinotti, Idalina M.M. de Carvalho, Adolfo I.B. Romo, Tércio de F. Paulo, Dieric S. Abreu, Marcelo Henrique Gehlen, Izaura C.N. Diógenes, Monilson P. dos Reis |
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| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Repositório Institucional da USP (Biblioteca Digital da Produção Intelectual) Universidade de São Paulo (USP) instacron:USP |
| Popis: | Photophysical studies of 4′-methyl-2,2′-bipyridine derivatized with the polycyclic aromatic hydrocarbons (PAHs) anthracene (mbpy-anth), naphthalene (mbpy-naph), and pyrene (mbpy-pyr) were acquired in different solvents. While the absorption spectra were not affected by the solvent nature, the emission ones showed red shifts with increase polarity consistent with an intramolecular charge-transfer (ICT) character. Theoretical calculations found a dominant “Hole” → “Particle” contribution for the first five transitions involving local excited-state (LE) and intramolecular charge-transfer (ICT) transitions, with the latter being dominant at higher wavelengths (S0 → 1CT). The fluorescence solvatochromic data suggested a hybridized local and charge transfer (HLCT) state for the mbpy-R compounds with the CT contribution prevailing in high polar solvents; a result that was corroborated by the monoexponential decay lifetimes. The Stokes shifts difference between heptane and dimethylsulphoxide, the most and least polar solvents used in this work, was calculated as 1315, 2969, and 808 cm−1 for mbpy-naph, mbpy-anth, and mbpy-pyr, respectively. The increase of the solvent polarity results in a red shift and a broadening of the emission and excitation bands for mbpy-anth and mbpy-naph with the spectra of the latter being the most affected. For mbpy-pyr, on the contrary, the emission spectra were narrower than the excitation ones indicating the La transitions lie at lower energy than the Lb. For this species, the results indicated an effective mixing of LE and CT states in the moderately polar solvents being in accordance with the observed single exponential decay which is likely related to one hybridized state. |
| Databáze: | OpenAIRE |
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