Application of 12080-32-9. The mechanism of aromatic electrophilic substitution of aromatic heterocycles is consistent with that of benzene. Compound: Dichloro(1,5-cyclooctadiene)platinum(II), is researched, Molecular C8H12Cl2Pt, CAS is 12080-32-9, about Understanding Doping Effects on Electronic Structures of Gold Superatoms: A Case Study of Diphosphine-Protected M@Au12 (M = Au, Pt, Ir). Author is Hirai, Haru; Takano, Shinjiro; Nakamura, Toshikazu; Tsukuda, Tatsuya.
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, the authors synthesized unprecedented [IrAu12(dppe)5Cl2]+ [IrAu12; dppe = 1,2-bis(diphenylphosphino)ethane] and [PtAu12(dppe)5Cl2]2+ (PtAu12) and compared their electronic structures with that of [Au13(dppe)5Cl2]3+ (Au13). Single-crystal x-ray diffractometry, 31P{1H} NMR, and Ir L3-edge extended X-ray absorption fine structure anal. of IrAu12 revealed that the single Ir atom is located at the center of the icosahedral IrAu12 core. Electrochem. anal. demonstrated that the energy levels of the highest occupied MOs are upshifted in the order of Au13 < PtAu12 < IrAu12. This trend was qual. 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-. IrAu12 underwent reversible redox reactions between the charge states of 1+ and 2+. The gradual increase of the energy gap between the HOMO and LUMO in the order of Au13 < PtAu12 < IrAu12 was observed by electrochem. measurement and optical spectroscopy. This study provides a simple guiding principle to tune the electronic structures of heterometal-doped superatoms. The orbital energies of [IrAu12(dppe)5Cl2]+ (IrAu12) and [PtAu12(dppe)5Cl2]2+ (PtAu12) were compared with those of [Au13(dppe)5Cl2]3+ (Au13) by electrochem. anal. The superat. orbitals were shifted up in the order of IrAu12 > PtAu12 > Au13. The result was explained by the upshift of the bottom of the effective potential due to different formal charge states of the dopants. Whereas Au was incorporated as Au+, Ir and Pt were incorporated as Ir- and Pt0, resp.
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