Effect of Selenium Substitution on Intersystem Crossing in π-Conjugated Donor-Acceptor-Donor Chromophores: The LUMO Matters the Most

The Journal of Physical Chemistry Letters
Rajendra AcharyaKirk S Schanze

Abstract

This study explores the effect of substitution of selenium (Se) for sulfur (S) on the photophysical properties of a series of π-conjugated donor-acceptor-donor chromophores based on 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT). The effect of Se substitution is studied systematically, where the substitution is in the thiophene donors only, the benzothiadiazole acceptor only, and in all of the positions. The fluorescence quantum yield decreases with an increase in Se substitution. Nanosecond-microsecond transient absorption and singlet oxygen sensitization experiments show that the effect of Se is due to an increase in the rate and efficiency of intersystem crossing with increased Se substitution. The relationship between intersystem crossing efficiency and heteroatom substitution pattern shows that the effects are largest when the heavy atom Se is in the acceptor benzothiadiazole unit. DFT calculations support the hypothesis that the effect arises because the LUMO is concentrated in the acceptor moiety, enhancing the spin-orbit coupling effect imparted by the Se atom.

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Citations

Jun 1, 2017·ACS Applied Materials & Interfaces·Jakob WudarczykKlaus Müllen
Nov 20, 2016·Chemical Communications : Chem Comm·Hang PanWeian Zhang
Feb 25, 2020·Chemical Communications : Chem Comm·Guo-Bin HuangXiang-Kui Ren
Aug 15, 2020·Chemical Society Reviews·Devika SasikumarMahesh Hariharan
Apr 5, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Laila A Al-MutabaganiKhulood A Abu Al-Ola
May 22, 2021·Physical Chemistry Chemical Physics : PCCP·Jie YangZe-Sheng Li
Aug 25, 2018·The Journal of Physical Chemistry. a·Enrico PomaricoAntonín Vlček
Mar 14, 2019·Journal of the American Chemical Society·Shunjie LiuBen Zhong Tang
Mar 7, 2019·The Journal of Physical Chemistry Letters·Ran LiuGuozhen Zhang

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