Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer

Ma, Lin1,2; Kuang, Zhuoran1,2; Wang, Zeming1,2; Zhao, Hongmei1,2; Wan, Yan3; Zhang, Xian -Fu4; Li, Yang1,2; Xia, Andong1,2

2023

10.1021/acs.jpclett.2c03581

Journal of Physical Chemistry Letters   Impact Factor & Quartile

1948-7185

In this work, the photoinduced charge separation (CS) via symmetry breaking in an orthogonal meso-beta-linked boron dipyrromethene (BODIPY) dimer was investigated by polarized transient absorption spectroscopy. The time constant about 0.76 ps of the CS reaction determined in dimethyl sulfoxide is much faster than the solvation dynamics. The observed transient anisotropy of the BODIPY anion band implies that both hole and electron transfers occur with similar probabilities. The bidirectional charge transfer processes suggest that the locally excited state is weakly coupled to the polar solvent, and the solvation coupled excited-state structural relaxation within the BODIPY monomeric unit is rather limited. In combination with the electronic excitation analysis based on time-dependent density-functional theory calculations, we deduced that the CS in the orthogonal BODIPY dimer is enabled via the torsional motion associated with covalently connected BODIPY units, promoting the electronic coupling, and irrelevant to the dynamic solvent relaxation.

SCI

English

NI Journal Papers

Corresponding

National Natural Science Foundation of China (NSFC)["22133001","21827803","22203009","21873013","62074073"]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Atomic, Molecular & Chemical

WOS:000921820300001

AMER CHEMICAL SOC

Web of Science

1.Beijing Univ Posts & Telecommun BUPT, State Key Lab Informat Photon & Opt Commun, Beijing 100876, Peoples R China
2.Beijing Univ Posts & Telecommun BUPT, Sch Sci, Beijing 100876, Peoples R China
3.Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China
4.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Guangdong, Peoples R China

Ma, Lin,Kuang, Zhuoran,Wang, Zeming,et al. Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer[J]. Journal of Physical Chemistry Letters,2023.

Ma, Lin.,Kuang, Zhuoran.,Wang, Zeming.,Zhao, Hongmei.,Wan, Yan.,...&Xia, Andong.(2023).Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer.Journal of Physical Chemistry Letters.

Ma, Lin,et al."Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer".Journal of Physical Chemistry Letters (2023).