Photoprocesses in bis(18-crown-6)-1, 3-distyrylbenzene and its complexes with metal perchlorates. (January 2021)

• Record Type: Journal Article
• Authors: Atabekyan, Levon S.; Freidzon, Alexandra Ya; Chibisov, Alexander K.; Gromov, Sergey P.; Vatsadze, Sergey Z.; Nuriev, Vyacheslav N.; Medvedko, Alexey V.
• Is Part Of: Dyes and pigments. Volume 184(2021)
• Publication Date: 2021-01
• Subjects: 1, 3-distyrylbenzene -- Fluorescence -- Complexation -- Laser flash photolysis -- Triplet state -- Quantum chemical calculations -- DFT and TDDFT calculations -- Excited states; Dyes and dyeing -- Periodicals; Pigments -- Periodicals; 667.2
• DOI: 10.1016/j.dyepig.2020.108773
• Languages: English
• ISSNs: 0143-7208

Abstract

Abstract: Photoprocesses of bis(18-crown-6)-1, 3-distyrylbenzene (DSB) and its complexes with barium and lead perchlorates in a MeCN–CH2 Cl2 (9:1, v/v) mixture were studied by absorption, luminescence, and laser kinetic spectroscopies. Unlike its strongly conjugated 1, 4-isomer, 1, 3-derivative shows almost independent behavior of its chromophoric subunits and is capable of phototransformations not observed in 1, 4-distyrylbenzenes. Triplet DSB complexes are involved in the radiationless deactivation of the excited state along with the fluorescence processes. The most effective intersystem crossing was observed for the complex with lead perchlorate. The process is accompanied by a drastic decrease in the quantum yield of DSB fluorescence. Quantum chemistry (DFT and TDDFT) is used to calculate the geometric structure and absorption spectra of DSB and its complexes with barium and lead cations and to explain the observed results. Highlights: The nano- and microsecond kinetics of bis(18-crown-6)-1, 3-distyrylbenzene and its complexes with Ba2+ and Pb2+ is studied. 1, 3-Distyrylbenzenes show independent behavior of their chromophoric subunits and are capable of novel phototransformations. Quantum chemistry explains the experimental data. The results are useful for the rational design of photoswitches and sensors.