Synergistic photoredox and copper catalysis by diode-like coordination polymer with twisted and polar copper–dye conjugation

• Published in: Nature communications Vol. 11; no. 1; p. 5384
• Main Authors: Shi, Yusheng, Zhang, Tiexin, Jiang, Xiao-Ming, Xu, Gang, He, Cheng, Duan, Chunying
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 23.10.2020; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/77/887; 639/638/77/890; 639/638/911; Adaptability; Catalysis; Circuits; Conjugation; Coordination polymers; Copper; Couplings; Dyes; Electron transfer; Fluorescence; Humanities and Social Sciences; Ligands; multidisciplinary; Nucleophiles; Photoreduction; Polymers; Quenching; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-19172-3

Synergistic photoredox and copper catalysis confers new synthetic possibilities in the pharmaceutical field, but is seriously affected by the consumptive fluorescence quenching of Cu(II). By decorating bulky auxiliaries into a photoreductive triphenylamine-based ligand to twist the conjugation between the triphenylamine-based ligand and the polar Cu(II)–carboxylate node in the coordination polymer, we report a heterogeneous approach to directly confront this inherent problem. The twisted and polar Cu(II)–dye conjunction endows the coordination polymer with diode-like photoelectronic behaviours, which hampers the inter- and intramolecular photoinduced electron transfer from the triphenylamine - moiety to the Cu(II) site and permits reversed-directional ground-state electronic conductivity, rectifying the productive loop circuit for synergising photoredox and copper catalysis in pharmaceutically valuable decarboxylative C(sp 3 )–heteroatom couplings. The well-retained Cu(II) sites during photoirradiation exhibit unique inner-spheric modulation effects, which endow the couplings with adaptability to different types of nucleophiles and radical precursors under concise reaction conditions, and distinguish the multi-olefinic moieties of biointeresting steride derivatives in their late-stage trifluoromethylation-chloration difunctionalisation. Synergistic photoredox–copper catalysis is limited by fluorescence quenching of Cu(II) ions to photoreductive dyes in solution. Here, the authors compromise photoreduction and Cu(II) catalysis by diode-like coordination polymer with twisted Cu(II)–dye conjugation, revealing its vast application vistas.