Issue 38, 2024

Atomically precise rhodium–indium carbonyl nanoclusters: synthesis, characterization, crystal structure and electron-sponge features

Abstract

In this paper we present the investigation of the reactivity of [Rh7(CO)16]3− with InCl3, with the aim of expanding the more general study that allowed us to obtain, among other species, the icosahedral [Rh12E(CO)27]n (n = 4 when E = Ge or Sn; n = 3 when E = Sb or Bi) family of clusters. Indeed, the study resulted in the isolation and characterization of the analogous In-centred icosahedral [Rh12In(CO)28]3− nanocluster (1), which is isoelectronic and isostructural with the [Rh12E(CO)27]n congeners. During the course of the reaction two more new species, namely the octahedral [Rh6(CO)15InCl3]2− (2) and the dimeric [{Rh6(CO)15InCl2}2]2− (3) have also been identified. The reaction between [Rh7(CO)16]3− and InCl3 proved to be poorly selective; nevertheless, by fine tuning some reaction parameters it was possible to drive the reaction more towards one product or the other. Alternatively, [Rh6(CO)15InCl3]2− can be more selectively prepared by reacting either [Rh5(CO)15] or, less efficiently, [Rh6(CO)15]2− with InCl3. As for the dimeric [{Rh6(CO)15InCl2}2]2− species, this was only isolated by carrying out the reaction with [Rh7(CO)16]3− under inert atmosphere, as opposed to under CO. All clusters were characterized by IR spectroscopy and ESI-MS, and their molecular structures were fully established by single-crystal X-ray diffraction studies. The [Rh12In(CO)28]3− species was also analysed by EDS via SEM, and further investigated through in situ infrared spectroelectrochemistry and CV experiments to check its multivalence nature. Indeed, [Rh12In(CO)28]3− can reversibly undergo two monoelectronic oxidation and one bi-electronic reduction processes, behaving like an electron sponge and, thus, giving rise to the further [Rh12In(CO)28]n derivatives (n = 1, 2 and 5). These results parallel the findings for the [Rh12E(CO)27]n series. The geometry variations of the metal framework associated with the changes in the cluster negative charge were investigated by means of DFT calculations.

Graphical abstract: Atomically precise rhodium–indium carbonyl nanoclusters: synthesis, characterization, crystal structure and electron-sponge features

Supplementary files

Article information

Article type
Paper
Submitted
14 Jul 2024
Accepted
27 Aug 2024
First published
28 Aug 2024
This article is Open Access
Creative Commons BY license

Nanoscale, 2024,16, 17852-17867

Atomically precise rhodium–indium carbonyl nanoclusters: synthesis, characterization, crystal structure and electron-sponge features

G. Bussoli, A. Boccalini, M. Bortoluzzi, C. Cesari, M. C. Iapalucci, T. Funaioli, G. Scorzoni, S. Zacchini, S. Ruggieri and C. Femoni, Nanoscale, 2024, 16, 17852 DOI: 10.1039/D4NR02922D

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