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

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• 作者：Jesse L. Guillet ; Indrani Bhowmick ; Matthew P. Shores ; Christopher J. A. Daley ; Milan Gembicky ; James A. Golen ; Arnold L. Rheingold ; Linda H. Doerrer
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 15, 2016
• 年：2016
• 卷：55
• 期：16
• 页码：8099-8109
• 全文大小：559K
• 年卷期：0
• ISSN：1520-510X

文摘

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)₂Na}⁺ variants, none of which form extended structures. In contrast, neutral [PtCr(tba)₄(NCS)]_∞ 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.