Understanding the excited-state charge transfer/separation (CT/CS) of donor-π-acceptor chromophores can provide guidance for designing and synthesizing advanced dyes to improve the performance of dye-sensitized solar cells (DSSCs) in practical applications. Herein, two newly synthesized electronic push–pull molecules, CS-14 and CS-15, that consist of carbazole donor and benzothiadiazole acceptor segments are chosen to explore the ultrafast dynamics of intramolecular CT/CS processes. The theoretical calculation results depict an excited-state intramolecular CT character for both dyes, while the dihedral angle between donor and acceptor of CS-14 is larger than that of CS-15, suggesting a more significant CT character of CS-14. Furthermore, compared to CS-14, the bond rotation of CS-15 between donor and π-bridge is restricted by employing the hexatomic ring, indicating the stronger molecular planarization of CS-15. Ultrafast spectroscopy clearly shows a solvent polarity-dependent excited-state species evolution from CT to CS—the CT character is observed in low-polar toluene solvent, while the feature of the CS state in polar tetrahydrofuran and acetone solvents is captured, which successfully proved a solvent polarity modulated excited-state CT/CS characters. We also found that though the generation of the CS state within CS-14 is slightly faster than that of CS-15, the charge recombination process of CS-15 with excellent planar conformation is much slower, providing enough time for a higher charge migration efficiency in DSSCs.
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7 May 2022
Research Article|
May 04 2022
Conformation-related excited-state charge transfer/separation of donor-π-acceptor chromophores
Special Collection:
Photophysics in Emerging Photovoltaics
Jie Kong;
Jie Kong
1
School of Science, Beijing University of Posts and Telecommunications (BUPT)
, Beijing 100876, People’s Republic of China
2
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences
, Beijing 100190, People’s Republic of China
3
Department of Chemical Physics, University of Science and Technology of China
, Hefei, Anhui 230026, People’s Republic of China
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Wei Zhang
;
Wei Zhang
1
School of Science, Beijing University of Posts and Telecommunications (BUPT)
, Beijing 100876, People’s Republic of China
2
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences
, Beijing 100190, People’s Republic of China
3
Department of Chemical Physics, University of Science and Technology of China
, Hefei, Anhui 230026, People’s Republic of China
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Xiaomin Zhang;
Xiaomin Zhang
4
Hebei Key Laboratory of Organic Functional Molecules, College of Chemistry and Material Science, Hebei Normal University
, No. 20, East Road of Nan Er Huan, Shijiazhuang 050024, People’s Republic of China
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Bo Liu;
Bo Liu
a)
4
Hebei Key Laboratory of Organic Functional Molecules, College of Chemistry and Material Science, Hebei Normal University
, No. 20, East Road of Nan Er Huan, Shijiazhuang 050024, People’s Republic of China
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Yang Li;
Yang Li
b)
1
School of Science, Beijing University of Posts and Telecommunications (BUPT)
, Beijing 100876, People’s Republic of China
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Andong Xia
Andong Xia
c)
1
School of Science, Beijing University of Posts and Telecommunications (BUPT)
, Beijing 100876, People’s Republic of China
2
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences
, Beijing 100190, People’s Republic of China
c)Author to whom correspondence should be addressed: andongxia@bupt.edu.cn
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a)
Electronic address: liubo@hebtu.edu.cn
b)
Electronic address: liyang1988@bupt.edu.cn
c)Author to whom correspondence should be addressed: andongxia@bupt.edu.cn
Note: This paper is part of the JCP Special Topic on Photophysics in Emerging Photovoltaics.
J. Chem. Phys. 156, 174902 (2022)
Article history
Received:
March 24 2022
Accepted:
April 19 2022
Citation
Jie Kong, Wei Zhang, Xiaomin Zhang, Bo Liu, Yang Li, Andong Xia; Conformation-related excited-state charge transfer/separation of donor-π-acceptor chromophores. J. Chem. Phys. 7 May 2022; 156 (17): 174902. https://doi.org/10.1063/5.0092880
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