Metal-Organic Cages Assembled From {Ni6} Nodes for Selective CO2 Reduction

Man Ting Lv; Meng Di Cui; Kai Peng Bai; Yu Jiang; Wei Peng Chen; Na Na Sun; Xiang Quan Hu; Chang Huang; Qing Yuan Yang; Yan Zhen Zheng

doi:10.1002/anie.202506838

Metal-Organic Cages Assembled From {Ni₆} Nodes for Selective CO₂ Reduction

Man Ting Lv
, Meng Di Cui
, Kai Peng Bai
, Yu Jiang
, Wei Peng Chen
, Na Na Sun
, Xiang Quan Hu
, Chang Huang
, Qing Yuan Yang
, Yan Zhen Zheng

Xi'an Jiaotong University

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

9 Scopus citations

Abstract

Constructing cluster-based nodes and using them as catalytic sites can bring new structure and function for metal-organic cages (MOCs). However, successful examples are very limited. Herein, we found that a 2-mercapto-5-methyl-1,3,4-thiadiazole (Hmmt) based {Ni₆} subunit is robust in building such MOCs. The {Ni₆} node is based on the central Ni₄ cubane and two wing Ni(II) ions with virtually three or four connected features. When various carboxylate ligands are incorporated the triangular prismatic [Ni₁₈(Hmmt)₃(mmt)₁₂(BPDC)₆(CH₃O)₁₂(H₂O)₆(DMF)₆] (4/MOC-18N, H₂BPDC = biphenyl-4,4′-dicarboxylic acid), tetrahedral-like [Ni₂₄(Hmmt)₄(mmt)₁₆(BTC)₄(CH₃O)₁₆Cl₄(H₂O)₄(DMF)₅(CH₃OH)₃] (5/MOC-24N, H₃BTC = 1,3,5-benzenetricarboxylic acid) and the octahedral [Ni₃₆(Hmmt)₆(mmt)₂₄(BTC)₈(CH₃O)₂₄(H₂O)₁₂(DMF)₁₂] (6/MOC-36N) can be isolated. Interestingly, MOCs 4–6 can uptake CO₂ in solid states. Moreover, they can effectively and selectively convert CO₂ into CO under visible light owing to the active wing Ni(II) ions, which are ancillarily coordinated with solvent molecules. All of them show turnover frequencies larger than 3500 µmol·g⁻¹·h⁻¹ and selectivity higher than 90%. This is a much higher performance compared to the usage of cage space for CO₂ reduction in previously reported MOCs and competitive to most Ni(II)-based simple coordination complexes. As such, this work may open a new paradigm for designing node based catalytic function for MOCs.

Original language	English
Article number	e202506838
Journal	Angewandte Chemie - International Edition
Volume	64
Issue number	27
DOIs	https://doi.org/10.1002/anie.202506838
State	Published - 1 Jul 2025

Keywords

CO reduction
Metal-organic cage
Photocatalytic
Self-assembly

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@article{a3ff257dd7644f3d92b68a6e653362a5,

title = "Metal-Organic Cages Assembled From \{Ni6\} Nodes for Selective CO2 Reduction",

abstract = "Constructing cluster-based nodes and using them as catalytic sites can bring new structure and function for metal-organic cages (MOCs). However, successful examples are very limited. Herein, we found that a 2-mercapto-5-methyl-1,3,4-thiadiazole (Hmmt) based \{Ni6\} subunit is robust in building such MOCs. The \{Ni6\} node is based on the central Ni4 cubane and two wing Ni(II) ions with virtually three or four connected features. When various carboxylate ligands are incorporated the triangular prismatic [Ni18(Hmmt)3(mmt)12(BPDC)6(CH3O)12(H2O)6(DMF)6] (4/MOC-18N, H2BPDC = biphenyl-4,4′-dicarboxylic acid), tetrahedral-like [Ni24(Hmmt)4(mmt)16(BTC)4(CH3O)16Cl4(H2O)4(DMF)5(CH3OH)3] (5/MOC-24N, H3BTC = 1,3,5-benzenetricarboxylic acid) and the octahedral [Ni36(Hmmt)6(mmt)24(BTC)8(CH3O)24(H2O)12(DMF)12] (6/MOC-36N) can be isolated. Interestingly, MOCs 4{\textendash}6 can uptake CO2 in solid states. Moreover, they can effectively and selectively convert CO2 into CO under visible light owing to the active wing Ni(II) ions, which are ancillarily coordinated with solvent molecules. All of them show turnover frequencies larger than 3500 µmol·g−1·h−1 and selectivity higher than 90\%. This is a much higher performance compared to the usage of cage space for CO2 reduction in previously reported MOCs and competitive to most Ni(II)-based simple coordination complexes. As such, this work may open a new paradigm for designing node based catalytic function for MOCs.",

keywords = "CO reduction, Metal-organic cage, Photocatalytic, Self-assembly",

author = "Lv, \{Man Ting\} and Cui, \{Meng Di\} and Bai, \{Kai Peng\} and Yu Jiang and Chen, \{Wei Peng\} and Sun, \{Na Na\} and Hu, \{Xiang Quan\} and Chang Huang and Yang, \{Qing Yuan\} and Zheng, \{Yan Zhen\}",

note = "Publisher Copyright: {\textcopyright} 2025 Wiley-VCH GmbH.",

year = "2025",

month = jul,

day = "1",

doi = "10.1002/anie.202506838",

language = "英语",

volume = "64",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

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TY - JOUR

T1 - Metal-Organic Cages Assembled From {Ni6} Nodes for Selective CO2 Reduction

AU - Lv, Man Ting

AU - Cui, Meng Di

AU - Bai, Kai Peng

AU - Jiang, Yu

AU - Chen, Wei Peng

AU - Sun, Na Na

AU - Hu, Xiang Quan

AU - Huang, Chang

AU - Yang, Qing Yuan

AU - Zheng, Yan Zhen

PY - 2025/7/1

Y1 - 2025/7/1

N2 - Constructing cluster-based nodes and using them as catalytic sites can bring new structure and function for metal-organic cages (MOCs). However, successful examples are very limited. Herein, we found that a 2-mercapto-5-methyl-1,3,4-thiadiazole (Hmmt) based {Ni6} subunit is robust in building such MOCs. The {Ni6} node is based on the central Ni4 cubane and two wing Ni(II) ions with virtually three or four connected features. When various carboxylate ligands are incorporated the triangular prismatic [Ni18(Hmmt)3(mmt)12(BPDC)6(CH3O)12(H2O)6(DMF)6] (4/MOC-18N, H2BPDC = biphenyl-4,4′-dicarboxylic acid), tetrahedral-like [Ni24(Hmmt)4(mmt)16(BTC)4(CH3O)16Cl4(H2O)4(DMF)5(CH3OH)3] (5/MOC-24N, H3BTC = 1,3,5-benzenetricarboxylic acid) and the octahedral [Ni36(Hmmt)6(mmt)24(BTC)8(CH3O)24(H2O)12(DMF)12] (6/MOC-36N) can be isolated. Interestingly, MOCs 4–6 can uptake CO2 in solid states. Moreover, they can effectively and selectively convert CO2 into CO under visible light owing to the active wing Ni(II) ions, which are ancillarily coordinated with solvent molecules. All of them show turnover frequencies larger than 3500 µmol·g−1·h−1 and selectivity higher than 90%. This is a much higher performance compared to the usage of cage space for CO2 reduction in previously reported MOCs and competitive to most Ni(II)-based simple coordination complexes. As such, this work may open a new paradigm for designing node based catalytic function for MOCs.

AB - Constructing cluster-based nodes and using them as catalytic sites can bring new structure and function for metal-organic cages (MOCs). However, successful examples are very limited. Herein, we found that a 2-mercapto-5-methyl-1,3,4-thiadiazole (Hmmt) based {Ni6} subunit is robust in building such MOCs. The {Ni6} node is based on the central Ni4 cubane and two wing Ni(II) ions with virtually three or four connected features. When various carboxylate ligands are incorporated the triangular prismatic [Ni18(Hmmt)3(mmt)12(BPDC)6(CH3O)12(H2O)6(DMF)6] (4/MOC-18N, H2BPDC = biphenyl-4,4′-dicarboxylic acid), tetrahedral-like [Ni24(Hmmt)4(mmt)16(BTC)4(CH3O)16Cl4(H2O)4(DMF)5(CH3OH)3] (5/MOC-24N, H3BTC = 1,3,5-benzenetricarboxylic acid) and the octahedral [Ni36(Hmmt)6(mmt)24(BTC)8(CH3O)24(H2O)12(DMF)12] (6/MOC-36N) can be isolated. Interestingly, MOCs 4–6 can uptake CO2 in solid states. Moreover, they can effectively and selectively convert CO2 into CO under visible light owing to the active wing Ni(II) ions, which are ancillarily coordinated with solvent molecules. All of them show turnover frequencies larger than 3500 µmol·g−1·h−1 and selectivity higher than 90%. This is a much higher performance compared to the usage of cage space for CO2 reduction in previously reported MOCs and competitive to most Ni(II)-based simple coordination complexes. As such, this work may open a new paradigm for designing node based catalytic function for MOCs.

KW - CO reduction

KW - Metal-organic cage

KW - Photocatalytic

KW - Self-assembly

UR - https://www.scopus.com/pages/publications/105004202831

U2 - 10.1002/anie.202506838

DO - 10.1002/anie.202506838

M3 - 文章

C2 - 40271936

AN - SCOPUS:105004202831

SN - 1433-7851

VL - 64

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 27

M1 - e202506838

ER -

Metal-Organic Cages Assembled From {Ni₆} Nodes for Selective CO₂ Reduction

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Keywords

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