A homologous series of macrocyclic Ni clusters: synthesis, structures, and catalytic properties

Huixin Xiang; Ranran Cheng; Chenhao Ruan; Changqing Meng; Yuzheng Gan; Wanyu Cheng; Yue Zhao; Cong-Qiao Xu; Jun Li; Chuanhao Yao

doi:10.1039/d3nr06015b

A homologous series of macrocyclic Ni clusters: synthesis, structures, and catalytic properties

Nanoscale. 2024 Feb 29;16(9):4563-4570. doi: 10.1039/d3nr06015b.

Authors

Huixin Xiang^{1

2}, Ranran Cheng², Chenhao Ruan^{1

2}, Changqing Meng^{1

2}, Yuzheng Gan^{1

2}, Wanyu Cheng¹, Yue Zhao³, Cong-Qiao Xu⁴, Jun Li^{4

5}, Chuanhao Yao^{1

2}

Affiliations

¹ Strait Institute of Flexible Electronics, Fujian Normal University, Fuzhou 350117, China. ifechhyao@fjnu.edu.cn.
² Institute of Flexible Electronics (IFE), Northwestern Polytechnical University, Xi'an 710072, China.
³ Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
⁴ Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China. xucq@sustech.edu.cn.
⁵ Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing 10084, China.

PMID: 38305474
DOI: 10.1039/d3nr06015b

Abstract

Due to their intriguing ring structures and promising applications, nickel-thiolate clusters, such as [Ni_n(SR)_2n] (n = 4-6), have attracted tremendous interest. However, investigation of the synthesis, structures, and properties of macrocyclic Ni_n clusters (n > 8) has been seriously impeded. In this work, a homologous series of macrocyclic nickel clusters, Ni_n(4MPT)_2n (n = 9-12), was fabricated by using 4-methylphenthiophenol (4MPT) as the ligand. The structures and compositions of the clusters were determined by single-crystal X-ray diffraction (SXRD) in combination with electrospray ionization mass spectrometry (ESI-MS). Experimental results and theoretical calculations show that the electronic structures of the clusters do not change significantly with the increase of Ni atoms. The coordination interactions between Ni and S atoms in [NiS₄] subunits are proved to play a crucial rule in the remarkable stability of Ni clusters. Finally, these clusters display excellent catalytic activity towards the reduction of p-nitrophenol, and a linear correlation between catalytic activity and ring size was revealed. The study provides a facile approach to macrocyclic homoleptic nickel clusters, and contributes to an in-depth understanding of the structure-property correlations of nickel clusters at the atomic level.