hotophysical properties of push-pi-pull type chromophores of aryl-substituted bipyridines in different solvent

Autor(es)

Bezerra, Lucas F. ^[1] ; Reis, Monilson P. ^[1] ; Romo, Adolfo I. B. ^{[1, 2]} ; Abreu, Dieric S. ^{[1, 3]} ; Gehlen, Marcelo H. ^[4] ; Longhinotti, Elisane ^[5] ; Paulo, Tercio F. ^[1] ; Carvalho, Idalina M. M. ^[1] ; Diogenes, Izaura C. N. ^[1]

Afiliação do(s) autor(es)

^[1] Univ Fed Ceara, Ctr Ciencias, Dept Quim Organ & Inorgan, Lab Bioinorgan, Fortaleza, Ceara - Brazil

^[2] Univ Illinois, Dept Chem, Urbana, IL 61801 - USA

^[3] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Lab Espect Mol, Av Prof Lineu Prestes 748, Sao Paulo, SP - Brazil

^[4] Univ Sao Paulo, Inst Quim Sao Carlos, Sao Carlos, SP - Brazil

^[5] Univ Fed Ceara, Ctr Ciencias, Dept Quim Analit & Fisicoquim, Fortaleza, Ceara - Brazil

• Tipo de documento: Artigo Científico
• Fonte: JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY; v. 425, MAR 1 2022.
• Citações Web of Science: 0

Resumo

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 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 mbpypyr, 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 mbpypyr, 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. (AU)

• Processo FAPESP: 19/21939-0 - Nanopartículas anisotrópicas bimetálicas (Au/Pd) para investigação de processos catalíticos através de espectroscopia Raman intensificada por superfície (SERS)
• Beneficiário: Dieric dos Santos de Abreu
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado