NDLI: DFT studies on the influence of ligation on optical and redox properties of bimetallic [Au<sub>4</sub>M<sub>2</sub>] clusters

Content Provider	Royal Society of Chemistry (RSC)
Author	Pillegowda, Manohar Periyasamy, Ganga
Copyright Year	2016
Abstract	Density functional theory based calculations have been employed to understand the lowest energy conformers of bare [Au4M2] and ligated [Au4M2(SCH3)6] and [Au4M2(PH3)6]2+ (where M = Au, Cu, Ag, Ni, Pd, Pt) clusters in the gas phase and in various implicit solvent media (water, DMSO and DCM). Computations predict that [Au4M2] clusters in all three charge states exist with a planar 2D-geometry, with distortion introduced by the hetero atoms. And the studies show that the ligation promotes a 2D to 3D geometrical conversion either through bridging coordination or single bond formation. The sulfur atom in the thiol ligand becomes a part of the cluster skeleton, while the PH3 forms a passivation layer around the cluster. Moreover, the presence of sulfur in the cluster skeleton increases the chemical stability of coinage metal containing clusters, while stability decreases for d8 metal containing clusters. And the PH3 passivation layer decreases the chemical stability of both coinage metal and d8 metal atom containing clusters. The computed redox behaviors show that the addition of an electron requires less energy compared to that needed for removal, and both occur with negligible geometrical reorganisation. The calculated blue shift in excitation energy values show a ligand to metal charge transfer in the –SCH3 ligated cluster. However, the red shift in wavelength is observed for the –PH3 passivated cluster, which corresponds to excitation from the HOMO to LUMO, where the orbitals have an equal contribution from the metals and ligands.
Starting Page	86051
Ending Page	86060
Page Count	10
File Format	HTM / HTML PDF
ISSN	20462069
Volume Number	6
Issue Number	89
Journal	RSC Advances
DOI	10.1039/c6ra14886g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Thiol HOMO\/LUMO DMSO Ligand HOMO Redox Wavelength Three-dimensional space Blueshift Dimethyl sulfoxide Covalent bond Density functional theory Sulfur Solvent Passivation (chemistry)
Content Type	Text
Resource Type	Article
Subject	Chemistry Chemical Engineering

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