Journal
NANOSCALE
Volume 10, Issue 40, Pages -Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8nr04078h
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Funding
- Japan Society for the Promotion of Science (JSPS) KAKENHI [JP16H04099, 16K21402, 17H05385]
- Takahashi Industrial and Economic Research Foundation
- Futaba Electronics Memorial Foundation
- Iwatani Naoji Foundation
- Ube Industries Foundation
- Asahi Glass Foundation
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division
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A recent study implied that a hetero-biicosahedral 25-atom cluster composed of two kinds of icosahedral 13-atom clusters could serve as a molecular rectifier and dipole material. However, no hetero-biicosahedral 25-atom clusters containing three types of ligands, in this case, phosphines, halogens, and thiolates, have been reported. In this study, we selectively synthesized [Au24Pd(PPh3)(10)(SC2H4Ph)(5)Cl-2]Cl (Au = gold, Pd = palladium, PPh3 = triphenylphosphine, SC2H4Ph = phenylethanethiolate, Cl = chloride), in which one Au was replaced with a Pd. The single-crystal X-ray structural analysis demonstrated that [Au24Pd(PPh3)(10)(SC2H4Ph)(5)Cl-2]Cl was a hetero-biicosahedral 25-atom cluster in which the central atom of one icosahedral Au-13 core was replaced by a Pd atom. Optical absorption spectroscopy suggested that the electronic structure of each individual icosahedral 13-atom core in [Au24Pd(PPh3)(10)(SC2H4Ph)(5)Cl-2](+) was reasonably well maintained, similar to the case of [Au-25(PPh3)(10)(SC2H4Ph)(5)Cl-2](2+). Density functional theory calculation revealed that the peak splitting in the region below 2.2 eV of the optical absorption spectrum of [Au24Pd(PPh3)(10)(SC2H4Ph)(5)Cl-2](+) is due to the splitting of HOMOs and also suggested that this cluster has dipole moment. Electrochemical measurements showed that [Au24Pd(PPh3)(10)(SC2H4Ph)(5)Cl-2](+) was relatively stable to reduction. These results are expected to contribute to the development of molecular rectifiers and dipole materials based on hetero-biicosahedral 25-atom clusters.
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