Coinage Metal Complexes Supported by the Tri- and
Tetraphosphine Ligands
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Abstract
A series of tri-
and tetranuclear phosphine complexes of d<sup>10</sup> metal ions
supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine
(<i>PPP</i>) and tris(diphenylphosphinomethyl)phosphine
(<i>PPPP</i>), were synthesized. All the compounds under
study, [AuM<sub>2</sub>(<i>PPP</i>)<sub>2</sub>]<sup>3+</sup> (M = Au (<b>1</b>), Cu (<b>2</b>), Ag (<b>3</b>)), [M<sub>4</sub>(<i>PPPP</i>)<sub>2</sub>]<sup>4+</sup> (M = Ag (<b>4</b>), Au (<b>5</b>)), [AuAg<sub>3</sub>(<i>PPPP</i>)<sub>2</sub>]<sup>4+</sup> (<b>6</b>), and [Au<sub>2</sub>Cu<sub>2</sub>(<i>PPPP</i>)<sub>2</sub>(NCMe)<sub>4</sub>]<sup>4+</sup> (<b>7</b>), were characterized
crystallographically. The trinuclear clusters <b>1</b>–<b>3</b> contain a linear metal core, while in the isostructural
tetranuclear complexes <b>4</b>–<b>6</b> the metal
framework has a plane star-shaped arrangement. Cluster <b>7</b> adopts a structural motif that involves a digold unit bridged by
two arms of the <i>PPPP</i> phosphines and decorated two
spatially separated Cu<sup>I</sup> ions chelated by the remaining
P donors. The NMR spectroscopic investigation in DMSO solution revealed
the heterometallic clusters <b>2</b>, <b>3</b>, and <b>6</b> are stereochemically nonrigid and undergo reversible metal
ions redistribution between several species, accompanied by their
solvation–desolvation. The complexes <b>1</b>–<b>3</b> and <b>5</b>–<b>7</b> exhibit room temperature
luminescence in the solid state (Φ<sub>em</sub> = 6–64%)
in the spectral region from 450 to 563 nm. The phosphorescence observed
originates from the triplet excited states, determined by the metal
cluster-centered d<sub>σ*</sub> → p<sub>σ</sub> transitions