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

Due to their intriguing ring structures and promising applications, nickel-thiolate clusters, such as [Ni(SR)₂] (n = 4-6), have attracted tremendous interest. However, investigation of the synthesis, structures, and properties of macrocyclic Ni clusters (n > 8) has been seriously impeded. In this work, a homologous series of macrocyclic nickel clusters, Ni(4MPT)₂ (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.