Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg₂₄(SR)₁₈]^2– (M = Pd, Pt) Clusters

Abstract

With the incorporation of Pd or Pt atoms, thiolated Ag-rich 25-metal-atom nanoclusters were successfully prepared and structurally characterized for the first time. With a composition of [PdAg24(SR)18](2-) or [PtAg24(SR)18](2-), the obtained 25-metal-atom nanoclusters have a metal framework structure similar to that of widely investigated Au25(SR)18. In both clusters, a M@Ag12 (M = Pd, Pt) core is capped by six distorted dimeric -RS-Ag-SR-Ag-SR- units. However, the silver-thiolate overlayer gives rise to a geometric chirality at variance to Au25(SR)18. The effect of doping on the electronic structure was studied through measured optical absorption spectra and ab initio analysis. This work demonstrates that modulating electronic structures by transition-metal doping is expected to provide effective means to manipulate electronic, optical, chemical, and catalytic properties of thiolated noble metal nanoclusters.

Switching a Nanocluster Core from Hollow to Nonhollow

“…The typical routes for metal NC synthesis are: i) direct reduction of metal precursors in the presence of desired ligands, [22][23][24][25][26][27][28] ii) postsynthetic ligand-exchange (LE), [29][30][31][32][33][34][35] and iii) metal-exchange 15,[36][37][38][39][40][41] . Among these methods, LE has recently been widely adopted for preparing novel gold NCs [42][43][44] .…”

Asymmetric Synthesis of Chiral Bimetallic [Ag28Cu12(SR)24]4– Nanoclusters via Ion Pairing

“…The majority of chiral metal nanoclusters known to date are of types (a) [27][28][29][30][31][32][33][34][35][36] and (b) 16,17,[37][38][39] , with a few belonging to types (c) and (d). [40][41][42] As prepared, many of these chiral metal nanoclusters (types b-d) are racemic mixtures that require separation and purification by various optical resolution methods.…”

Potent in vitro antiproliferative properties for a triplatinum cluster toward triple negative breast cancer cells

“…A variety of Pt clusters were thus prepared and characterised mostly containing a number of Pt atoms ranging from 3 to 50 [5][6][7][8]. In spite of these intense research activities and of extensive literature reports, we realised that this kind of compounds were poorly considered for their biological actions.…”