Silva Rafaela A L, Santos Rodrigo, Andrade Marta M, Santos Isabel C, Coutinho Joana T, Pereira Laura C J, Waerenborgh João C, Vieira Bruno J C, Cirera Jordi, Ruiz Eliseo, Almeida Manuel, Belo Dulce
Departament de Quı́mica Inorgànica i Orgànica, Institut de Quı́mica Teòrica i Computacional, Diagonal 645, 08028 Barcelona, Spain.
Inorg Chem. 2020 Jul 6;59(13):9261-9269. doi: 10.1021/acs.inorgchem.0c01154. Epub 2020 Jun 16.
Tetraphenylphosphonium salts of Co and Fe complexes with alkyl-substituted, -butyl (), and isopropyl () 2,3-thiophenedithiolate (α-tpdt) ligands, namely, TPP[Co(α--tpdt)] (), TPP[Fe(α--tpdt)] (-), TPP[Co(α--tpdt)] (), and TPP[Fe(α--tpdt)] () were prepared and characterized by cyclic voltammetry, single crystal X-ray diffraction, magnetic susceptibility measurements, and Fe Mössbauer spectroscopy. Compound and are isostructural with their Au and Ni analogues with a square-planar coordination geometry. Compound presents two polymorphs (-) both showing a Fe(III) bisdithiolene dimerization. The magnetic susceptibility of and exhibits behavior dominated by antiferromagnetic interactions, with room-temperature magnetic moments of 3.40 and 3.36 μB, respectively, indicating that these square-planar Co(III) complexes assume an intermediate spin electronic configuration ( = 1) as supported by multiconfigurational and DFT calculations.
钴和铁与烷基取代的、正丁基（）和异丙基（）2,3 - 噻吩二硫醇盐（α - tpdt）配体形成的配合物的四苯基鏻盐，即TPP[Co(α - -tpdt)]（）、TPP[Fe(α - -tpdt)]（ - ）、TPP[Co(α - -tpdt)]（）和TPP[Fe(α - -tpdt)]（），通过循环伏安法、单晶X射线衍射、磁化率测量和铁穆斯堡尔光谱进行了制备和表征。化合物和与其金和镍类似物同构，具有平面正方形配位几何结构。化合物呈现两种多晶型物（ - ），均显示出Fe(III)双二硫烯二聚化。和的磁化率表现出以反铁磁相互作用为主导的行为，室温磁矩分别为3.40和3.36 μB，表明这些平面正方形Co(III)配合物呈现中间自旋电子构型（ = 1），这得到了多组态和密度泛函理论计算的支持。
