Assembling Phenothiazine into a Porous Coordination Cage to Improve Its Photocatalytic Efficiency for Organic Transformations

Lin, Hengyu; Xiao, Zhifeng; Le, Khoa N.; Yan, Tian‐hao; Cai, Peiyu; Yang, Yihao; Day, Gregory S.; Drake, Hannah F.; Xie, Haomiao; Bose, Riya; Ryan, Conor A.; Hendon, Christopher H.; Zhou, Hong‐Cai

doi:10.1002/anie.202214055

Assembling Phenothiazine into a Porous Coordination Cage to Improve Its Photocatalytic Efficiency for Organic Transformations

Journal Article · 09 November 2022 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202214055· OSTI ID:2422644

^[1]; Xiao, Zhifeng ^[1]; Le, Khoa N. ^[2]; Yan, Tian‐hao ^[1]; Cai, Peiyu ^[1]; Yang, Yihao ^[1]; Day, Gregory S. ^[1]; Drake, Hannah F. ^[1]; Xie, Haomiao ^[1]; Bose, Riya ^[3]; Ryan, Conor A. ^[3]; ^[2]; ^[1]

Department of Chemistry Texas A&,M University College Station TX 77843 USA
Department of Chemistry University of Oregon Eugene OR 97403 USA
Department of Physics University of Texas at Dallas 800 W. Campbell Rd. Richardson TX 75080 USA

Abstract

Photo‐catalysis by small‐molecules is often limited by catalyst degradation and low electron‐transfer efficiency. Herein we report a stable N‐phenyl‐phenothiazine (PTH)‐derived porous coordination cage (PCC) as a highly efficient photocatalyst. By the incorporation of the photocatalytic PTH moiety into a PCC, aggregation‐induced quenching (AIQ) was shown to be reduced. An improvement in catalyst stability was discovered, ascribed to the synergistic effects of the PTH moieties. The catalyst, operating through a photolytic single‐electron transfer, was utilized for photo‐catalyzed dehalogenation and borylation. Evaluation of the catalytic mechanism in the borylation reaction showed that the improved performance results from the more efficient formation of the electron donor‐acceptor (EDA) complex with the cage. This discovery provides a potential strategy to improve the photophysical properties and stabilities of small‐molecule organic photocatalysts via supramolecular chemistry.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 2422644

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 61; ISSN 1433-7851

Publisher:: Wiley

Country of Publication:: United States

Language:: English

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