| Summary: | A decanuclear silver chalcogenide cluster, [Ag<sub>10</sub>(Se){Se<sub>2</sub>P(O<i><sup>i</sup></i>Pr)<sub>2</sub>}<sub>8</sub>] (<b>2</b>) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag<sub>7</sub>(H){Se<sub>2</sub>P(O<i><sup>i</sup></i>Pr)<sub>2</sub>}<sub>6</sub>], under thermal condition. The time-dependent NMR spectroscopy showed that <b>2</b> was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [Cu<sub>x</sub>Ag<sub>10-x</sub>(Se){Se<sub>2</sub>P(O<i><sup>i</sup></i>Pr)<sub>2</sub>}<sub>8</sub>] (x = 0–7, <b>3</b>), via heating [Cu<sub>x</sub>Ag<sub>7−x</sub>(H){Se<sub>2</sub>P(O<i><sup>i</sup></i>Pr)<sub>2</sub>}<sub>6</sub>] (x = 1–6) at 60 °C. Compositions of <b>3</b> were accurately confirmed by the ESI mass spectrometry. While the crystal <b>2</b> revealed two un-identical [Ag<sub>10</sub>(Se){Se<sub>2</sub>P(O<i><sup>i</sup></i>Pr)<sub>2</sub>}<sub>8</sub>] structures in the asymmetric unit, a co-crystal of [Cu<sub>3</sub>Ag<sub>7</sub>(Se){Se<sub>2</sub>P(O<i><sup>i</sup></i>Pr)<sub>2</sub>}<sub>8</sub>]<sub>0.6</sub>[Cu<sub>4</sub>Ag<sub>6</sub>(Se){Se<sub>2</sub>P(O<i><sup>i</sup></i>Pr)<sub>2</sub>}<sub>8</sub>]<sub>0.4</sub> ([<b>3a</b>]<sub>0.6</sub>[<b>3b</b>]<sub>0.4</sub>) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of <b>2</b>, [<b>3a</b>]<sub>0.6</sub>[<b>3b</b>]<sub>0.4</sub> and the previous published [Ag<sub>10</sub>(Se){Se<sub>2</sub>P(OEt)<sub>2</sub>}<sub>8</sub>] (<b>1</b>) are quite similar (10 metals, 1 Se<sup>2−</sup>, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism.
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