A series of simple [Pt(SCN)] salts with a variety of cations was synthesized and characterized using X-ray crystallography to determine factors that could induce platinophilic interactions between [Pt(SCN)] anions, including cation size and shape, charge, and ability to participate in hydrogen bonding. The salts [N(PPh)][Pt(SCN)], [AsPh][Pt(SCN)], and [Co(1,10-phenanthroline)][Pt(SCN)] feature bulky, noncoordinating cations where the [Pt(SCN)] anions are completely separated from each other, with no Pt-Pt interactions present. Salts containing the hydrogen-bonding cations [Co(NH)][Pt(SCN)] and [Co(en)][Pt(SCN)] (en = 1,2-ethylenediamine) display close Pt-Pt distances, with both compounds exhibiting platinophilic interactions with distances of 3.373(2) and 3.539(8) Å, respectively, the first reported platinophilic interactions with the [Pt(SCN)] unit. [Co(en)][Pt(SCN)] also presents intermolecular chalcogen S···S and Pt···S interactions, resulting in increased dimensionality while also assisting in assembling the platinophilic interaction. The compounds are emissive at 77 K in the solid state, exhibiting a d-d metal-centered transition regardless of whether or not any platinophilic interactions are present. Overall, hydrogen-bonding cations are most likely to promote close proximity of the Pt(II) metal centers and induce the formation of platinophilic interactions in [Pt(SCN)].
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