jz7b01052_si_001.pdf (1.49 MB)
Au22Ir3(PET)18: An Unusual Alloy Cluster through Intercluster Reaction
journal contribution
posted on 2017-06-06, 00:00 authored by Shridevi Bhat, Ananya Baksi, Sathish Kumar Mudedla, Ganapati Natarajan, V. Subramanian, Thalappil PradeepAn intercluster reaction
between Au25(PET)18 and Ir9(PET)6 producing the alloy cluster,
Au22Ir3(PET)18 exclusively, is demonstrated
where the ligand PET is 2-phenylethanethiol. Typical reactions of
this kind between Au25(PET)18 and Ag25(SR)18, and other clusters reported previously, produce
mixed cluster products. The cluster composition was confirmed by detailed
high-resolution electrospray ionization mass spectrometry (ESI MS)
and other spectroscopic techniques. This is the first example of Ir
metal incorporation in a monolayer-protected noble metal cluster.
The formation of a single product was confirmed by thin layer chromatography
(TLC). Density functional theory (DFT) calculations suggest that the
most favorable geometry of the Au22Ir3(PET)18 cluster is one wherein the three Ir atoms are arranged triangularly
with one Ir atom at the icosahedral core and the other two on the
icosahedral shell. Significant contraction of the metal core was observed
due to strong Ir–Ir interactions.
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TLCTypical reactionselectrospray ionization mass spectrometrymetal cluster22 Ir 3Significant contractionIr atomsspectroscopic techniqueslayer chromatographycluster compositionUnusual Alloy Clustericosahedral shellligand PETicosahedral coreDFTalloy clustermetal corecluster productsIntercluster ReactionIr atomIr 9ESI MSAg 2518 clusterintercluster reactionSR2- phenylethanethiolIr metal incorporation
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