Dependence of Excited-State Properties of a Low-Bandgap Photovoltaic Copolymer on Side-Chain Substitution and Solvent

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• 作者：Ning-Jiu Zhao ; Dr. Mao-Jie Zhang ; Dr. Ran Liang ; Dr. Li-Min Fu ; Dr. Wei Zhang ; Prof. Xi-Cheng Ai ; Prof. Jian-Hui Hou and Prof. Jian-Ping Zhang
• 刊名：ChemSusChem
• 出版年：2016
• 出版时间：July 7, 2016
• 年：2016
• 卷：9
• 期：13
• 页码：1623-1633
• 全文大小：2079K
• ISSN：1864-564X

文摘

The excited-state properties and chain conformations of a new low-bandgap copolymer based on benzo[1,2-b:4,5-b′]dithiophene (BDT) and thieno[3,4-b]thiophene with meta-alkoxyphenyl-substituted side chains in solution were investigated comprehensively. Time-resolved spectroscopy suggested that the excited-state properties were sensitive to the conformations of the copolymer in solution. In addition, excited-state dynamics analyses revealed the photogeneration of triplet excited states by intersystem crossing (ISC) at a rate constant of ∼0.4×10⁹ s⁻¹ as a result of direct meta-alkoxyphenyl connection to the donor unit BDT irrespective to the macromolecular conformations. According to El-Sayed's rule, the fast ISC herein is correlated with the change of orbital types between singlet and triplet excited states as also shown by quantum chemical calculations. Our studies may shed light on the structure–property relationships of photovoltaic materials.