Donor-acceptor fluorophores for energy-transfer-mediated photocatalysis

Triplet-triplet energy transfer (EnT) is a fundamental activation pathway in photocatalysis. In this work, we report the mechanistic origins of the triplet excited state of carbazole-cyanobenzene donor-acceptor (D-A) fluorophores in EnT-based photocatalytic reactions and demonstrate the key factors...

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Bibliographic Details
Main Authors: Lu, Jingzhi, Pattengale, Brian, Liu, Qiuhua, Yang, Sizhuo, Shi, Wenxiong, Li, Shuzhou, Huang, Jier, Zhang, Jian
Other Authors: School of Materials Science & Engineering
Format: Article
Language:English
Published: 2020
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Online Access:https://hdl.handle.net/10356/139338
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Institution: Nanyang Technological University
Language: English
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Summary:Triplet-triplet energy transfer (EnT) is a fundamental activation pathway in photocatalysis. In this work, we report the mechanistic origins of the triplet excited state of carbazole-cyanobenzene donor-acceptor (D-A) fluorophores in EnT-based photocatalytic reactions and demonstrate the key factors that control the accessibility of the 3LE (locally excited triplet state) and 3CT (charge-transfer triplet state) via a combined photochemical and transient absorption spectroscopic study. We found that the energy order between 1CT (charge transfer singlet state) and 3LE dictates the accessibility of 3LE/3CT for EnT, which can be effectively engineered by varying solvent polarity and D-A character to depopulate 3LE and facilitate EnT from the chemically more tunable 3CT state for photosensitization. Following the above design principle, a new D-A fluorophore with strong D-A character and weak redox potential is identified, which exhibits high efficiency for Ni(II)-catalyzed cross-coupling of carboxylic acids and aryl halides with a wide substrate scope and high selectivity. Our results not only provide key fundamental insight on the EnT mechanism of D-A fluorophores but also establish its wide utility in EnT-mediated photocatalytic reactions.