Directional Doping and Cocrystallizing an Open-Shell Ag₃₉ Superatom via Precursor Engineering

Abstract

Metal precursors employed in the bottom-up synthesis of metal nanoclusters (NCs) are of great importance in directing their composition and geometrical structure. In this work, a silver nanocluster co-protected by phosphine and thiolate, namely, [Ag39(PFBT)24(TPP)8]2– (Ag 39 , PFBT = pentafluorobenzenethiol, TPP = triphenylphosphine), was isolated and structurally characterized. It adopts a three-layered Ag13@Ag18@Ag8S24P8 core–shell structure. The Ag13@Ag18 kernel is unusual in multilayer noble metal NCs. By introducing a copper precursor in the synthesis, a bimetallic nanocluster [Ag37Cu2(PFBT)24(TPP)8]2– (Ag 37 Cu 2 ) with an identical structure to Ag 39 apart from two outer Ag atoms being substituted by Cu atoms was obtained. Astoundingly, the Cu precursor used in the synthesis was found to be critical in determining the final structure. The alteration of the Cu precursor led to the cocrystallization of the above alloy nanocluster with a Ag14 nanocluster, namely, [Ag37Cu2(PFBT)24(TPP)8]2–·[Ag14(PFBT)6(TPP)8] (Ag 37 Cu 2 ·Ag 14 ). The electronic structure analyzed by theoretical calculation reveals that Ag 39 is a 17-electron open-shell superatom. The optical absorption of Ag 39 , Ag 37 Cu 2 , and Ag 37 Cu 2 ·Ag 14 was compared and studied in detail. This work not only enriches the family of alloy metallic nanoclusters but also provides a metal NC-based cocrystal platform for in-depth study of its crystal growth and photophysical property.

Platonic and Archimedean solids in discrete metal-containing clusters

“…78g), co-protected by phosphine (PPh 3 ) and thiolate (HSPhF 5 = pentafluorobenzenethiol). 659 The metal arrangement (Ag(center)@Ag 12 (icosahedron)@Ag 18 @Ag 8 (cube)) of Ag 39 is consistent with our speculation, but the Ag 18 shell reveals vertex vacancy defects, deviating from the dodecahedron constructed by 20 vertices (Fig. 78h).…”

“…Some AgÁ Á ÁAg interactions and organic ligands have been omitted for clarity. (h) Intermediate vertex-deficient dodecahedral Ag 18 shell of Ag 39 659.…”

Electrocatalytic CO2 Reduction over Atomically Precise Metal Nanoclusters Protected by Organic Ligands

“…In addition to the Au- and Cu-based NCs catalysts, Ag-based NCs are also achieving more attentions in CO 2 RR because of their excellent CO selectivity, their relatively low cost, and more importantly, their well-defined atomic packing structures. − Very recently, the Tang group reported the smallest alkynyl-protected Ag 15 (CC- t Bu) 12 + NC (denoted as Ag 15 ; CC- t Bu = tert -butylacetylene), which had a bcc structure with a core–shell–shell Ag@Ag 8 @Ag 6 metal configuration (Figure a) . The Ag 15 NC was capped by 12 -CC- t Bu ligands, in which the surface of Ag atom was linearly coordinated with two -CC- t Bu ligands, forming a linear t Bu-CC–Ag–CC- t Bu staple.…”

Alloying and dealloying of Au18Cu32nanoclusters at precise locationsviacontrolling the electronegativity of substituent groups on thiol ligands

“…Controlled doping of metals can be achieved using a multiligand-induced method. [39][40][41][42][43][44][45][46][47] For example, in the synthesis of Au-Ag alloy clusters using mixed ligands ( phosphorus and halogen ligands), Au preferentially connects to P while Ag preferentially bonds to the halogen owing to the difference in binding energies. 15,23,[48][49][50][51][52][53] However, this strategy did not work in homologated clusters.…”