Issue 33, 2021

Evaluation of ultrasmall coinage metal M13(dppe)6 M = Cu, Ag, and Au clusters. Bonding, structural and optical properties from relativistic DFT calculations

Abstract

Ultrasmall ligand-protected clusters are prototypical species for evaluating the variation at the bottom of the nanoscale range. Here we explored the ultrasmall gold–phosphine M13(dppe)6 cluster, as a prototypical framework to gain insights into the fundamental similarities and differences between Au, Ag, and Cu, in the 1–3 nm size range, via relativistic DFT calculations. Different charge states involving 8- and 10-cluster electron (ce) species with a 1S21P6 and 1S21P61D2 configuration, leading to structural modification in the Au species between Au13(dppm)65+ and Au13(dppm)63+, respectively. Furthermore, this structural distortion of the M13 core is found to occur to a lower degree for the calculated Ag and Cu counterparts. Interestingly, optical properties exhibit similar main patterns along with the series, inducing a blue-shift for silver and copper, in comparison to the gold parent cluster. For 10-ce species, the main features of 8-ce are retained with the appearance of several weak transitions in the range. The ligand–core interaction is enhanced for gold counterparts and decreased for lighter counterparts resulting in the Au > Cu > Ag trend for the interaction stabilization. Hence, the Ag and Cu counterparts of the Au13(dppm)6 cluster appear as useful alternatives, which can be further explored towards different cluster alternatives for building blocks for nanostructured materials.

Graphical abstract: Evaluation of ultrasmall coinage metal M13(dppe)6 M = Cu, Ag, and Au clusters. Bonding, structural and optical properties from relativistic DFT calculations

Supplementary files

Article information

Article type
Paper
Submitted
02 jun. 2021
Accepted
20 jul. 2021
First published
20 jul. 2021

Phys. Chem. Chem. Phys., 2021,23, 18035-18043

Evaluation of ultrasmall coinage metal M13(dppe)6 M = Cu, Ag, and Au clusters. Bonding, structural and optical properties from relativistic DFT calculations

P. L. Rodríguez-Kessler, M. Rojas-Poblete and A. Muñoz-Castro, Phys. Chem. Chem. Phys., 2021, 23, 18035 DOI: 10.1039/D1CP02451E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements