Understanding Doping Effects on Electronic Structures of Gold Superatoms: A Case Study of Diphosphine-Protected M@Au12 (M = Au, Pt, Ir)

Inorganic Chemistry
Haru HiraiTatsuya Tsukuda

Abstract

Dopants into ligand-protected Au superatoms have been hitherto limited to group X-XII elements (Pt, Pd, Ag, Cu, Hg, and Cd). To expand the scope of the dopants to the group IX elements, we synthesized unprecedented [IrAu12(dppe)5Cl2]+ [IrAu 12 ; dppe = 1,2-bis(diphenylphosphino)ethane] and [PtAu12(dppe)5Cl2]2+ (PtAu 12 ) and compared their electronic structures with that of [Au13(dppe)5Cl2]3+ (Au 13 ). Single-crystal X-ray diffractometry, 31P{1H} NMR, and Ir L3-edge extended X-ray absorption fine structure analysis of IrAu 12 revealed that the single Ir atom is located at the center of the icosahedral IrAu12 core. Electrochemical analysis demonstrated that the energy levels of the highest occupied molecular orbitals are upshifted in the order of Au 13 < PtAu 12 < IrAu 12 . This trend was qualitatively explained in such a manner that the jellium core potential at the central position becomes shallower by replacing Au+ with Pt0 and further with Ir-. IrAu 12 underwent reversible redox reactions between the charge states of 1+ and 2+. The gradual increase of the energy gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital in the order of Au 13 < PtAu 12 < IrAu 12 was observed by electroch...Continue Reading

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