Theoretical investigations on the structure–property relationships of Au₁₃and Au_xM_13−xnanoclusters

Abstract

As a fundamental building block in ultrasmall, noble metal nanoclusters, icosahedral Au x M 13Àx structures have recently attracted extensive research interest. In this study, density functional theory (DFT) and time-dependant DFT calculations have been carried out to investigate the structure-property (optical and electronic) relationships of a series of Au 13 and Au x M 13Àx (M ¼ Au, Ag, Cu, and Pd) nanoclusters coprotected by phosphine and chloride ligands. It was found that the size of the peripheral ligands significantly affects the geometric structure: the larger exterior ligands (with a larger cone angle) result in relatively longer Au-M bond distances and weaker metallic interactions within the Au x M 13Àx core.Therefore, the optical peak (in the UV-vis spectrum) corresponding to the HOMO / LUMO transition red-shifts accordingly. When different foreign atom(s) are incorporated, the preferential doping site is different, and the electronic and optical structures alter accordingly.

Monoarsine-protected icosahedral cluster [Au13(AsPh3)8Cl4]+: comparative studies on ligand effect and surface reactivity with its stibine analogue

“…, HCl-induced convergence), 6,7,22,23 exploration of formation mechanisms, 24,25 tuning of electronic properties ( e.g. , by heterometal doping 26–29 ), and optical properties ( e.g. , NIR emission 6,7,30 and chiroptical activity 31–33 ), as well as further expansion of their potential applications ( e.g.…”

“…[18][19][20][21] It is therefore of importance to study the inuencing factors in depth on the geometric and electronic structures of the individual icosahedral Au 13 clusters. In this context, the past 15 years have rst witnessed a renewed interest in the typical phosphine-protected Au 13 clusters involving development of new synthetic routes (e.g., HCl-induced convergence), 6,7,22,23 exploration of formation mechanisms, 24,25 tuning of electronic properties (e.g., by heterometal doping [26][27][28][29] ), and optical properties (e.g., NIR emission 6,7,30 and chiroptical activity [31][32][33] ), as well as further expansion of their potential applications (e.g., photodynamic catalysis and nano-electronic devices). 34,35 More recently, comparative studies on several new types of Au 13 analogues protected by other pnictines (e.g., functionalized diphosphine, 36 phosphinous acid, 37 diarsine, 38 and monostibine [39][40][41] ) or mimics of pnictine (N-heterocyclic carbenes) [42][43][44][45][46][47] have also been extensively made both experimentally and theoretically.…”