Structures and Phosphorescence Properties of Triphosphine-Supported
Au<sub>2</sub>Ag<sub>2</sub> and Au<sub>8</sub>Ag<sub>4</sub> Alkynyl
Cluster Complexes
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Abstract
The synthesis, structure, and phosphorescence properties of two
families of triphosphine-supported Au(I)–Ag(I) heteronuclear
alkynyl cluster complexes with unprecedented Au<sub>2</sub>Ag<sub>2</sub> and Au<sub>8</sub>Ag<sub>4</sub> cluster structures are described.
The phosphorescence emission over the whole visible light region was
systematically tuned through modification of the electronic effects
in aromatic acetylide ligands to attain bright phosphorescence with
different luminescent colors. Introduction of electron-withdrawing
CF<sub>3</sub> to phenylacetylides results in the emission spectral
blue-shift, while it shows progressive red-shift upon introducing
electron-donating Bu<sup>t</sup>, OMe, or NMe<sub>2</sub>. As demonstrated
from both experimental and theoretical studies, the phosphorescence
arises primarily from <sup>3</sup>LLCT/<sup>3</sup>IL and Au<sub>2</sub>Ag<sub>2</sub>/Au<sub>8</sub>Ag<sub>4</sub> cluster-centered <sup>3</sup>[d→p] transitions