Assembling giant heterometallic cyclic coordination clusters {MnII2LnIII2}n (n = 6 and 8) for efficient photocatalytic hydrogen production
- 1Frontier Institute of Science and Technology, Interdisciplinary Research Center of Frontier science and technology, Xi'an Key Laboratory of Electronic Devices and Materials Chemistry, School of Future Technology, College of Forensic Medicine, School of Chemistry, Xi'an Jiaotong University Xi'an 710054 China
- 2School of Materials Science and Engineering, Shaanxi University of Technology Hanzhong 723001 China
Abstract
Heterometallic Mn–rare earth metal clusters with exceptional catalytic activity remain scarcely explored. Herein, two nanosized oxo/alkoxo-bridged cyclic coordination clusters (CCCs), namely {Mn12Ln12} and {Mn16Ln16}, were successfully isolated. These elegant supramolecular aggregates represent rare examples of Mn(ii)-containing 3d–4f clusters, as Mn(ii) ions are highly susceptible to aerial oxidation under alkaline conditions. Notably, {Mn16Ln16} constitutes the largest such cluster reported to date in terms of nuclearity. Interestingly, both CCCs are composed of repetitive {Mn2Ln2O4} structural units, and their structures have certain similarities to some characteristics of the cubic {CaMn4O5} oxygen-evolving center in photosystem II. Crucially, these clusters exhibit excellent stability in solvents and function as highly efficient homogeneous photocatalysts for H2 production. Specifically, {Mn12Gd12} achieves an outstanding photocatalytic hydrogen production rate of 2778 µmol g−1 h−1, surpassing that of many reported covalent organic frameworks (COFs) and precious-metal-free inorganic photocatalysts. This superior catalytic performance stems from its suitable energy levels, high charge-transfer efficiency, and abundance of active oxygen sites. This work offers new mechanistic insights and design principles for the rational development of highly active manganese-cluster-based photocatalysts.
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BibTeX
@article{bai2026assembling,
title = {{Assembling giant heterometallic cyclic coordination clusters MnII2LnIII2n (n = 6 and 8) for efficient photocatalytic hydrogen production}},
author = {Kai-Peng Bai and Yu Wang and Wei-Peng Chen and Yuan-Qi Zhai and Qian-Cheng Luo and Xiang-Quan Hu and Yan-Zhen Zheng},
journal = {Chemical Science},
year = {2026},
month = sep,
doi = {10.1039/d6sc06444b},
url = {https://doi.org/10.1039/d6sc06444b},
note = {CC BY 3.0},
}
RIS
TY - JOUR
TI - Assembling giant heterometallic cyclic coordination clusters {MnII2LnIII2}n (n = 6 and 8) for efficient photocatalytic hydrogen production
AU - Kai-Peng Bai
AU - Yu Wang
AU - Wei-Peng Chen
AU - Yuan-Qi Zhai
AU - Qian-Cheng Luo
AU - Xiang-Quan Hu
AU - Yan-Zhen Zheng
PY - 2026
DA - 2026/09/15
JO - Chemical Science
DO - 10.1039/d6sc06444b
UR - https://doi.org/10.1039/d6sc06444b
AB - Heterometallic Mn–rare earth metal clusters with exceptional catalytic activity remain scarcely explored. Herein, two nanosized oxo/alkoxo-bridged cyclic coordination clusters (CCCs), namely {Mn12Ln12} and {Mn16Ln16}, were successfully isolated. These elegant supramolecular aggregates represent rare examples of Mn(ii)-containing 3d–4f clusters, as Mn(ii) ions are highly susceptible to aerial oxidation under alkaline conditions. Notably, {Mn16Ln16} constitutes the largest such cluster reported to date in terms of nuclearity. Interestingly, both CCCs are composed of repetitive {Mn2Ln2O4} structural units, and their structures have certain similarities to some characteristics of the cubic {CaMn4O5} oxygen-evolving center in photosystem II. Crucially, these clusters exhibit excellent stability in solvents and function as highly efficient homogeneous photocatalysts for H2 production. Specifically, {Mn12Gd12} achieves an outstanding photocatalytic hydrogen production rate of 2778 µmol g−1 h−1, surpassing that of many reported covalent organic frameworks (COFs) and precious-metal-free inorganic photocatalysts. This superior catalytic performance stems from its suitable energy levels, high charge-transfer efficiency, and abundance of active oxygen sites. This work offers new mechanistic insights and design principles for the rational development of highly active manganese-cluster-based photocatalysts.
SN - 2041-6520
SN - 2041-6539
ER -