Molecular Structure-Intersystem Crossing Relationship of Heavy-Atom-Free BODIPY Triplet Photosensitizers.
A thiophene-fused BODIPY chromophore displays a large triplet-state quantum yield (ΦT = 63.7%). In contrast, when the two thienyl moieties are not fused into the BODIPY core, intersystem crossing (ISC) becomes inefficient and ΦT remains low (ΦT = 6.1%). First-principles calculations including spin-orbit coupling (SOC) were performed to quantify the ISC. We found larger SOC and smaller singlet-triplet energy gaps for the thiophene-fused BODIPY derivative. Our results are useful for studies of the photochemistry of organic chromophores.
‡State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-208 West Campus, 2 Ling Gong Road, Dalian 116024, P. R. China.
Shaomin
S
Ji
‡State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-208 West Campus, 2 Ling Gong Road, Dalian 116024, P. R. China.
Jie
J
Ge
§CEISAM UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
Daniel
D
Escudero
‡State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-208 West Campus, 2 Ling Gong Road, Dalian 116024, P. R. China.
Zhijia
Z
Wang
‡State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-208 West Campus, 2 Ling Gong Road, Dalian 116024, P. R. China.
Jianzhang
J
Zhao
§CEISAM UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.|∥Institut Universitaire de France, 103 boulevard St Michel, 75005 Paris Cedex 5, France.
Denis
D
Jacquemin