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

Liuzhuang Xing, Qian Yang, Chen Zhu, Yilian Bai, Yurong Tang^*, Magnus Rueping^*, Yunfei Cai^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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.

Original language	English (US)
Article number	1501
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-023-37113-8
State	Published - Dec 2023

Bibliographical note

Funding Information:
This work is supported by funding from the Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX1105 to Y.C., CSTB2022NSCQ-MSX1032 to Y.T.), the National Natural Science Foundation of China (Grant no. 21801030 to Y.C.), the King Abdullah University of Science and Technology (KAUST), Saudi Arabia, Office of Sponsored Research (URF/1/4025 to C.Z. and M.R.). We thank the Analytical and Testing Center of Chongqing University for assistance with NMR spectrum analysis.

Funding Information:
This work is supported by funding from the Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX1105 to Y.C., CSTB2022NSCQ-MSX1032 to Y.T.), the National Natural Science Foundation of China (Grant no. 21801030 to Y.C.), the King Abdullah University of Science and Technology (KAUST), Saudi Arabia, Office of Sponsored Research (URF/1/4025 to C.Z. and M.R.). We thank the Analytical and Testing Center of Chongqing University for assistance with NMR spectrum analysis.

Publisher Copyright:
© 2023, The Author(s).

ASJC Scopus subject areas

General Chemistry
General Biochemistry, Genetics and Molecular Biology
General Physics and Astronomy

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title = "Poly(heptazine imide) ligand exchange enables remarkable low catalyst loadings in heterogeneous metallaphotocatalysis",

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

author = "Liuzhuang Xing and Qian Yang and Chen Zhu and Yilian Bai and Yurong Tang and Magnus Rueping and Yunfei Cai",

note = "Funding Information: This work is supported by funding from the Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX1105 to Y.C., CSTB2022NSCQ-MSX1032 to Y.T.), the National Natural Science Foundation of China (Grant no. 21801030 to Y.C.), the King Abdullah University of Science and Technology (KAUST), Saudi Arabia, Office of Sponsored Research (URF/1/4025 to C.Z. and M.R.). We thank the Analytical and Testing Center of Chongqing University for assistance with NMR spectrum analysis. Funding Information: This work is supported by funding from the Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX1105 to Y.C., CSTB2022NSCQ-MSX1032 to Y.T.), the National Natural Science Foundation of China (Grant no. 21801030 to Y.C.), the King Abdullah University of Science and Technology (KAUST), Saudi Arabia, Office of Sponsored Research (URF/1/4025 to C.Z. and M.R.). We thank the Analytical and Testing Center of Chongqing University for assistance with NMR spectrum analysis. Publisher Copyright: {\textcopyright} 2023, The Author(s).",

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AU - Tang, Yurong

AU - Rueping, Magnus

AU - Cai, Yunfei

N1 - Funding Information: This work is supported by funding from the Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX1105 to Y.C., CSTB2022NSCQ-MSX1032 to Y.T.), the National Natural Science Foundation of China (Grant no. 21801030 to Y.C.), the King Abdullah University of Science and Technology (KAUST), Saudi Arabia, Office of Sponsored Research (URF/1/4025 to C.Z. and M.R.). We thank the Analytical and Testing Center of Chongqing University for assistance with NMR spectrum analysis. Funding Information: This work is supported by funding from the Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX1105 to Y.C., CSTB2022NSCQ-MSX1032 to Y.T.), the National Natural Science Foundation of China (Grant no. 21801030 to Y.C.), the King Abdullah University of Science and Technology (KAUST), Saudi Arabia, Office of Sponsored Research (URF/1/4025 to C.Z. and M.R.). We thank the Analytical and Testing Center of Chongqing University for assistance with NMR spectrum analysis. Publisher Copyright: © 2023, The Author(s).

PY - 2023/12

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N2 - 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 (LnNi-PHI) have been prepared and fully characterized by various techniques including NMR, ICP-OES, XPS, HAADF-STEM and XAS. The LnNi-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 LnNi-PHI significantly enhances the photo/Ni dual catalytic activity, thus resulting in low catalyst loadings and high turnover numbers.

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

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

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