Citation: Ai Wang, Jun-Fei Bu, Ye Xia, Ming-Xing Chen, Xi Cheng, Feng Pan, Sisi Feng, Bing-Wu Wang, Song Gao. Diradicals induced long-lived charge-separated state in a photo-driven coordination molecular rotor: Crystal structure and photophysical response[J]. Chinese Chemical Letters, ;2026, 37(12): 112543. doi: 10.1016/j.cclet.2026.112543 shu

Diradicals induced long-lived charge-separated state in a photo-driven coordination molecular rotor: Crystal structure and photophysical response

Ai Wang ^{a, b} ,
Jun-Fei Bu ^b ,
Ye Xia ^c ,
Ming-Xing Chen ^d ,
Xi Cheng ^b ,
Feng Pan ^b ,
Sisi Feng ^a ,
Bing-Wu Wang ^{b, e, *,} ,
Song Gao ^{b, f, *,}

a.
Key Laboratory of Chemical Biology, Molecular Engineering of Ministry of Education, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China
b.
Beijing National Laboratory for Molecular Sciences College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
c.
Spin-X Institute, South China University of Technology, Guangzhou 511442, China
d.
Analytical Instrumentation Center College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
e.
School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China
f.
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, LIFM, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou 510275, China

wangbw@pku.edu.cn

gaosong@pku.edu.cn

Received Date: 8 December 2025
Revised Date: 1 February 2026
Accepted Date: 23 February 2026
Available Online: 23 February 2026

Figures(4)

Diradicals serve as efficient electron intermediaries and stabilizers, significantly retarding charge recombination to achieve a long-lived charge-separated state. The inherent instability and complicated relaxation dynamics of diradicals introduce considerable difficulties to the precise prediction and manipulation of their resultant molecular states. Herein, a novel coordination molecular rotor complex 1 adopts a rigid, dumbbell-shaped donor-acceptor (D–A) arrangement with minimized reorganization energy. Steady-state spectroscopy and nanosecond transient absorption spectroscopy reveal the photoinduced energy-transfer process and electron-transfer dynamics of complex 1 from zinc(Ⅱ) tetraphenylporphyrin (ZnTTP) to a perylenediimide derivative (BPPDI). Electron paramagnetic resonance spectroscopy under xenon lamp irradiation, together with theoretical calculations, demonstrates the formation of diradicals (ZnTTP^•+ and BPPDI^•−) during photo-induced charge separation, resulting in a long-lived charge-separated state with a lifetime exceeding 912 ns.
- Diradical,
- Photo-driven rotor,
- Coordination molecular rotor,
- Charge-separated state (CSS),
- Donor-acceptor (D-A) coordination system
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