Synthesis and Properties Evolution of a Family of Tiara-like Phenylethanethiolated Palladium Nanoclusters

• Published in: Scientific reports Vol. 5; no. 1; p. 16628
• Main Authors: Chen, Jishi, Liu, Liren, Weng, Linhong, Lin, Yuejian, Liao, Lingwen, Wang, Chengming, Yang, Jinlong, Wu, Zhikun
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 16.11.2015; Nature Publishing Group
• Subjects: 119/118; 140/146; 639/638/263/914; 639/925/357/354; Crystallography; Electrochemistry; Evolution; Humanities and Social Sciences; Laboratories; Ligands; Materials science; multidisciplinary; Palladium; Physics; Science; Single crystals; Sulfur; X-ray crystallography
• ISSN: 2045-2322; 2045-2322
• DOI: 10.1038/srep16628

Tiara-like thiolated group 10 transition metal (Ni, Pd, Pt) nanoclusters have attracted extensive interest due to their fundamental scientific significance and potential application in a number of fields. However, the properties ( e.g. the absorption) evolution with the ring size’s increase was not investigated so far to our best knowledge, due to the challenge of obtaining a series of nanocluster analogues. Herein, we successfully synthesized, isolated and identified a family of [Pd(SC 2 H 4 Ph) 2 ] n nanoclusters (totally 17 novel clusters, n = 4–20). Their structures were determined to be tiara-like by single crystal X-ray crystallography together with theoretical calculation; their formation mechanism was proposed to be a substitution—polycondensation—ring-closure process based on experimental observations. All of these clusters are rather robust (anti-reductive and anti-oxidative) owing to their tiara-like structures with large HOMO-LUMO gaps. Finally, the optical and electrochemical evolution with the increase of ring size was investigated and it is found that both optical and electrochemical gaps have a “turning point” at a size corresponding to n = 8 for [Pd(SR) 2 ] n nanoclusters.