Issue 1, 2022

Alloying dichalcogenolate-protected Ag21 eight-electron nanoclusters: a DFT investigation

Abstract

The isoelectronic doping of dichalcogenolato nanoclusters of the type [Ag21{E2P(OR)2}12]+ (E = S, Se) by any heteroatom belonging to groups 9–12 was systematically investigated using DFT calculations. Although they can differ in their global structure, all of these species have the same M@M12-centered icosahedral core. In any case, the different structure types are all very close in energy. In all of them, three different alloying sites can be identified (central, icosahedral, peripheral) and calculations allowed the trends in heteroatom site occupation preference across the group 9–12 family to be revealed. These trends are supported by complementary experimental results. They were rationalized on the basis of electronegativity, potential involvement in the bonding of valence d-orbitals and atom size. TD-DFT calculations showed that the effect of doping on optical properties is sizable and this should stimulate research on the modulation of luminescence properties in the dithiolato and diseleno families of complexes.

Graphical abstract: Alloying dichalcogenolate-protected Ag21 eight-electron nanoclusters: a DFT investigation

Supplementary files

Article information

Article type
Paper
Submitted
13 Sep 2021
Accepted
28 Nov 2021
First published
29 Nov 2021

Nanoscale, 2022,14, 196-203

Alloying dichalcogenolate-protected Ag21 eight-electron nanoclusters: a DFT investigation

F. Gam, I. Chantrenne, S. Kahlal, T. Chiu, J. Liao, C. W. Liu and J. Saillard, Nanoscale, 2022, 14, 196 DOI: 10.1039/D1NR06019H

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