open access

https://hdl.handle.net/2115/86509

Diarsine- vs diphosphine-protected Au-13 clusters : Effect of subtle geometric differences on optical property and electronic structure

英語

2021-08-07

American Institute of Physics (AIP)

Journal of Chemical Physics

155(5)

054301

In the design of ligand-protected metal clusters, the choice of protecting ligands is a critical factor because they can profoundly affect the nuclearity, geometry, and electronic structures to afford a diverse range of cluster compounds. Here, we report the synthesis of two novel diarsine-protected Au-13 clusters ([Au13L5Cl2](3+), L = diarsine) and compare these clusters with diphosphine analogs in terms of the core geometry and optical properties. In the crystal structure, the cluster bearing C3-bridged diarsines {[Au-13(dpap)(5)Cl-2](3+), 3} had an apparently identical icosahedral Au-13 core to [Au-13(dppe)(5)Cl-2](3+) (1) with C2-bridged diphosphines, but slight structural differences associated with the bridging unit of the ligands were found. Despite similar icosahedral Au-13 cores 1 and 3, their absorption and photoluminescence profiles were evidently different. Theoretical calculations revealed that the subtle deformation of the Au-13 icosahedron, rather than the coordinating atoms (As or P), notably influences the electronic structure to cause the difference in the absorption profiles.

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Version of Record

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Journal of Chemical Physics, 155(5), 07 August 2021, 054301 and may be found at https://doi.org/10.1063/5.0059607.

0021-9606

AA00694991