RESUMO
Due to their intriguing ring structures and promising applications, nickel-thiolate clusters, such as [Nin(SR)2n] (n = 4-6), have attracted tremendous interest. However, investigation of the synthesis, structures, and properties of macrocyclic Nin clusters (n > 8) has been seriously impeded. In this work, a homologous series of macrocyclic nickel clusters, Nin(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.
RESUMO
Doping Cd atom(s) into gold clusters is very promising in both theoretical study and practical applications. However, it has long been a challenge to synthesize heavily Cd-doped AuCd bimetallic clusters and thereby reveal their structure-property correlations. Herein a novel AuCd bimetallic cluster: Au16 Cd16 (SC6 H11 )20 (SC6 H11 denotes deprotonated cyclohexanethiol) with a Cd to Au atomic ratio of 1:1 is reported. The precise structure of the cluster determined by single crystal X-ray diffraction demonstrates that it has a unique hexatetrahedron Au14 core and a distinctive shell. Intriguingly, due to the special protecting motifs, the cluster exhibits high stability in various conditions studied, indicating that the geometric structure is crucial in determining the stability of the cluster. Most importantly, the photothermal property of the cluster has been investigated in comparison with those of M13 -kernel (M denotes metal atoms) clusters, and the results imply that the compactness and the Cd atom doping of the core play important roles in dictating the photothermal effect of the cluster. The authors believe that this work will provide some ideas for the rational design of clusters with high stability and excellent photothermal property.