Citation: Jianfang Cao, Xue Ma, Xinyu Chen, Tianci Zhang, Wen Sun. Theoretical perspective on fine-tuning ISC efficiency in D-A BODIPY photosensitizers through heteroatom incorporation and nitrogen ring strain modulation[J]. Chinese Chemical Letters, ;2025, 36(10): 110897. doi: 10.1016/j.cclet.2025.110897 shu

Theoretical perspective on fine-tuning ISC efficiency in D-A BODIPY photosensitizers through heteroatom incorporation and nitrogen ring strain modulation

Jianfang Cao ^{a, *,} ,
Xue Ma ^a ,
Xinyu Chen ^a ,
Tianci Zhang ^a ,
Wen Sun ^{b, *,}

a.
School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin Campus, Panjin 124221, China
b.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, High-tech District, Dalian 116024, China

caojf@dlut.edu.cn

sunwen@dlut.edu.cn

Received Date: 10 November 2024
Revised Date: 12 January 2025
Accepted Date: 20 January 2025
Available Online: 21 January 2025

Figures(4)

This study investigates the intersystem crossing (ISC) mechanism in donor-acceptor (D-A) type distyryl-BODIPY photosensitizers, including previously reported M1 (benzene donor), M2, M3 (phenothiazine donors), and newly predicted M4 (triphenylamine donor), M5-M7 (nitrogen-containing aliphatic rings with thiophene donors). Using computational chemistry, we analyzed their geometric configurations, spectral properties, spin-orbit coupling, and electron-hole orbitals. We found that S₂ is a charge transfer singlet state (¹CT), T₂ is a locally excited triplet state (³LE), and the S₂ → T₂ transition is the main ISC pathway in M2-M7, following the ¹CT → ³LE mechanism. M5-M7 show near-vertical dihedral angles between donor and acceptor in the S₂ state relative to M2-M4, facilitating charge transfer. The strain energies in the nitrogen-containing rings of M5-M7 affect oxidation potentials and ISC. M5, with the highest strain energy, shows the lowest oxidation potential, smaller ΔE_S2-T2, highest SOC, and fastest k_isc, making it the most efficient predicted singlet oxygen producer. This research clarifies the structure-performance relationships of near-infrared D-A type distyryl-BODIPY photosensitizers and provides a theoretical foundation for developing heavy-atom-free photosensitizers with tuned fluorescence quantum yield and singlet oxygen quantum yield.
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