Poly(heptazine imide) ligand exchange enables remarkable low catalyst loadings in heterogeneous metallaphotocatalysis.

Xing, Liuzhuang; Yang, Qian; Zhu, Chen; Bai, Yilian; Tang, Yurong; Rueping, Magnus; Cai, Yunfei · Nat Commun · 2023

basic_science · Level V

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Abstract

The development of heterogeneous metallaphotocatalysis is of great interest for sustainable organic synthesis. The rational design and controllable preparation of well-defined (site-isolated) metal/photo bifunctional solid catalysts to meet such goal remains a critical challenge. Herein, we demonstrate the incorporation of privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI). A variety of PHI-supported cationic bipyridyl-based Ni-catalysts (L<sub>n</sub>Ni-PHI) have been prepared and fully characterized by various techniques including NMR, ICP-OES, XPS, HAADF-STEM and XAS. The L<sub>n</sub>Ni-PHI catalysts exhibit exceptional chemical stability and recyclability in diverse C-P, C-S, C-O and C-N cross-coupling reactions. The proximity and cooperativity effects in L<sub>n</sub>Ni-PHI significantly enhances the photo/Ni dual catalytic activity, thus resulting in low catalyst loadings and high turnover numbers.