Synthesis and Luminescence Properties of Two-Electron Bimetallic Cu-Ag and Cu-Au Nanoclusters via Copper Hydride Precursors
Résumé
The synthesis, structural characteristics, and photophysical properties of luminescent Cu-rich bimetallic superatomic clusters [Au@Cu-12((S2CNPr2)-Pr-n)(6)(C CPh)(4)](+) (1a(+)), [Au@Cu-12{S2P(OR)(2)}(6)(C CPh)(4)](+) (2(+)), (2a(+) = Pr-i; 2b(+) = Pr-n), [Au@Cu-12{S2P(C2H4Ph)(2)}(6)(C CPh)(4)](+) (2c(+)), and [Ag@Cu-12{S2P((OPr)-Pr-n)(2)}(6)(C CPh)(4)](+) (3(+)) were studied. Compositionally uniform clusters 1(+)-3(+) were isolated from the reaction of dithiolato-stabilized, polyhydrido copper clusters with phenylacetylene in the presence of heterometal salts. By using X-ray diffraction, the structures of 1a(+), 2a(+), 2b(+), and 3(+) were able to be determined. ESI-mass spectrometry and elemental analysis confirmed their compositions and purity. The structural characteristics of these clusters are similar with respect to displaying gold (or silver)-centered Cu-12 cuboctahedra surrounded by six dithiocarbamate/dithiophosph(in)ate and four alkynyl ligands. The doping of Au and Ag atoms into the polyhydrido copper nanoclusters significantly enhances their PL quantum yields from Ag@Cu-12 (0.58%) to Au@Cu-12 (55%) at ambient temperature in solution. In addition, the electrochemical properties of the new alloys were investigated by cyclic voltammetry.
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Silalahi et al - 2021 - Synthesis and Luminescence Properties of Two-Electron.pdf (1.63 Mo)
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Silalahi_ic1c01489_si_001.pdf (3.61 Mo)
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