Plyuta Nataliya, Petrusenko Svitlana, Kokozay Vladimir N, Cauchy Thomas, Lloret Francesc, Julve Miguel, Cano Joan, Avarvari Narcis
Univ Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, France.
Department of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, Kyiv 01601, Ukraine.
Dalton Trans. 2022 Mar 22;51(12):4760-4771. doi: 10.1039/d1dt04274b.
A unique π-conjugated benzothiadiazole--vanillin ligand (HL), characterized by single crystal X-ray diffraction and DFT calculations, has been prepared by condensation between 4-amino-benzothiadiazole (BTD) and -vanillin. Its reaction with cobalt(II) acetate afforded the complex of formula [CoL]·CHCl (1), for which the coordination environment of the cobalt centre is a distorted octahedron and the ligand acts as a monoanionic tridentate chelate in its phenolate form. Intermolecular π-π stacking interactions between the π-conjugated BTD units provide an antiferromagnetic coupling pathway, as indicated by the analysis of the dc magnetic measurements of a crystalline sample of the complex and supported by DFT type calculations. The static magnetic behaviour of 1 is analysed according to spin-orbit coupling and zero-field splitting models. Remarkably, the complex exhibits slow relaxation of the magnetization under dc applied magnetic fields being thus a new example of field-induced mononuclear single-molecule magnet (SMM).
通过4-氨基苯并噻二唑（BTD）与香草醛缩合制备了一种独特的π共轭苯并噻二唑-香草醛配体（HL），通过单晶X射线衍射和密度泛函理论（DFT）计算对其进行了表征。它与醋酸钴（II）反应得到了化学式为[CoL]·CHCl₃的配合物（1），其中钴中心的配位环境为扭曲的八面体，配体以酚盐形式作为单阴离子三齿螯合物。π共轭BTD单元之间的分子间π-π堆积相互作用提供了一条反铁磁耦合途径，这由配合物晶体样品的直流磁性测量分析表明，并得到DFT类型计算的支持。根据自旋-轨道耦合和零场分裂模型对1的静态磁行为进行了分析。值得注意的是，该配合物在直流施加磁场下表现出磁化的缓慢弛豫，因此是场诱导单核单分子磁体（SMM）的一个新例子。
