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

Liuzhuang Xing; Qian Yang; Chen Zhu; Yilian Bai; Yurong Tang; Magnus Rueping; Yunfei Cai

doi:10.1038/s41467-023-37113-8

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

Nat Commun. 2023 Mar 17;14(1):1501. doi: 10.1038/s41467-023-37113-8.

Authors

Liuzhuang Xing^#¹, Qian Yang^#¹, Chen Zhu^#², Yilian Bai¹, Yurong Tang³, Magnus Rueping⁴, Yunfei Cai⁵

Affiliations

¹ School of Chemistry and Chemical Engineering, Chongqing University, 174 Shazheng Street, Chongqing, 400044, P. R. China.
² KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
³ School of Chemistry and Chemical Engineering, Chongqing University, 174 Shazheng Street, Chongqing, 400044, P. R. China. tangyuronga@cqu.edu.cn.
⁴ KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia. magnus.rueping@kaust.edu.sa.
⁵ School of Chemistry and Chemical Engineering, Chongqing University, 174 Shazheng Street, Chongqing, 400044, P. R. China. yf.cai@cqu.edu.cn.

^# Contributed equally.

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_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.

Abstract

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