A Twelve-Coordinated Iodide in a Cuboctahedral Silver(I)
Skeleton
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Abstract
Three new halide-centered
octanuclear silver(I) complexes, [Ag<sub>8</sub>(X){S<sub>2</sub>P(CH<sub>2</sub>CH<sub>2</sub>Ph)<sub>2</sub>}<sub>6</sub>](PF<sub>6</sub>), X = F<sup>–</sup>, <b>1</b>; Cl<sup>–</sup>, <b>2</b>; Br<sup>–</sup>, <b>3</b>; were prepared
in the presence of the corresponding halide anions with silver(I)
salts and dithiophosphinate ligands. Structure analyses displayed
that a Ag<sub>8</sub> cubic core can be modulated by the size effect
of the central halide; however, an iodide-centered Ag<sub>8</sub> cluster
was not found under similar reaction conditions. Interestingly, a
luminescent dodecanuclear silver(I) cluster, [Ag<sub>12</sub>(μ<sub>12</sub>-I)(μ<sub>3</sub>-I)<sub>4</sub>{S<sub>2</sub>P(CH<sub>2</sub>CH<sub>2</sub>Ph)<sub>2</sub>}<sub>6</sub>](I), <b>4</b>; was then synthesized. The structure of <b>4</b> contains
a novel μ<sub>12</sub>-I at the center of a cuboctahedral silver(I)
atom cage, which is further stabilized by four additional μ<sub>3</sub>-I and six dithiophosphinate ligands. To the best of our knowledge,
the μ<sub>12</sub>-I revealed in <b>4</b> is the highest
coordination number for a halide ion authenticated by both experimental
and computational studies. Previously, the μ<sub>12</sub>-I
was only observed in [PyH][{TpMo(μ<sub>3</sub>-S)<sub>4</sub>Cu<sub>3</sub>}<sub>4</sub>(μ<sub>12</sub>-I)]. The synthetic
details, spectroscopic studies including multinuclear NMR and ESI-MS,
structure elucidations by single crystal X-ray diffraction, and photoluminescence
of <b>4</b> are reported herein
