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_nNi-PHI) have been prepared and fully characterized by various techniques including NMR, ICP-OES, XPS, HAADF-STEM and XAS. The L_nNi-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_nNi-PHI significantly enhances the photo/Ni dual catalytic activity, thus resulting in low catalyst loadings and high turnover numbers.

多相金属光催化的发展对于可持续有机合成具有重要意义。合理设计和可控制备明确（位点隔离）的金属/光双功能固体催化剂来满足这一目标仍然是一个关键挑战。在此，我们证明了将独特的均相联吡啶基镍催化剂纳入高度有序的结晶钾聚七嗪酰亚胺（K-PHI）中。多种 PHI 负载的阳离子联吡啶基 Ni 催化剂 (L _n Ni-PHI) 已被制备并通过各种技术（包括 NMR、ICP-OES、XPS、HAADF-STEM 和 XAS）进行了充分表征。 L _n Ni-PHI 催化剂在各种 C−P、C−S、C−O 和 C−N 交叉偶联反应中表现出优异的化学稳定性和可回收性。 L _n Ni-PHI 中的邻近效应和协同效应显着增强了光/Ni 双催化活性，从而导致低催化剂负载量和高周转数。