Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer

A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)(4)(NCS)} have been prepared and thoroughly characterized. The {Na (15C5)} [PtM(SAc)(4)(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)(2))}[PtM(SAc)(4)(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M2+, necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)(2)Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)(4)(NCS)](infinity) 8 forms a coordination polymer of {PtCr} units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt...Pt interactions in the solid state. Four structural classes, one new, of {MPt}...{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/k(B) = 1.7(4) K.