Institut des Sciences Chimiques de Rennes, Université de Rennes, CNRS, UMR 6226, F-35000 Rennes, France.
Condensed Molecular Materials Laboratory, RIKEN, Wako-shi, Saitama 351-0198, Japan.
Inorg Chem. 2023 Mar 13;62(10):4197-4209. doi: 10.1021/acs.inorgchem.2c04300. Epub 2023 Feb 24.
Highly conducting, mixed-valence, multi-component nickel bis() salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)] (Me-thiazds: -methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (EtN and BuN PhP, respectively). This behavior strongly differs from that of the corresponding monoanionic complexes whose oxidation afforded the single component neutral species. This provides additional rare examples of mixed-valence conducting salts of nickel diselenolene complexes, only known in two examples with the dsit (1,3-dithiole-2-thione-4,5-diselenolate) and dsise (1,3-dithiole-2-selone-4,5-diselenolate) ligands. The mixed-valence salts form highly dimerized or trimerized bi- and trimetallic units, rarely seen with such nickel complexes. Transport measurements under a high pressure (up to 10 GPa) and band structure calculations confirm the semiconducting character of [PhP][Ni(Me-thiazds)] and the metallic character of [EtN][Ni(Me-thiazds)] and [NBu][Ni(Me-thiazds)] salts (0 < < 1).
通过单阴离子物种[Ni(Me-thiazds)]（Me-thiazds：-甲基-1,3-噻唑啉-2-硫酮-4,5-二硒代）的电结晶，获得了高导电、混合价、多组分镍双（）盐，其化学计量比为 1:2 和 1:3，具体取决于所使用的抗衡离子（分别为 EtN 和 BuN PhP）。这种行为与相应的单阴离子配合物的氧化行为有很大的不同，后者氧化得到单一成分的中性配合物。这提供了镍二硒烯配合物混合价导电盐的另外几个罕见例子，仅在两个具有 dsit（1,3-二硫代-2-硫酮-4,5-二硒代）和 dsise（1,3-二硫代-2-硒酮-4,5-二硒代）配体的例子中已知。混合价盐形成高度二聚或三聚的双金属和三金属单元，这种镍配合物很少见。在高压力（高达 10 GPa）下的输运测量和能带结构计算证实了[PhP][Ni(Me-thiazds)]的半导体性质以及[EtN][Ni(Me-thiazds)]和[NBu][Ni(Me-thiazds)]盐（0 < < 1）的金属性质。
