Rodríguez-Jiménez Santiago, Brooker Sally
Department of Chemistry and MacDiarmid Institute for Advanced Materials and Nanotechnology , University of Otago , P.O. Box 56, Dunedin 9054 , New Zealand.
Inorg Chem. 2019 Jun 17;58(12):8188-8197. doi: 10.1021/acs.inorgchem.9b01006. Epub 2019 May 24.
The pyridazine-pyridine triazole-based Rat ligand, L [4-(4-methylphenyl)-3-(3-pyridazinyl)-5-(2-pyridinyl)-1,2,4-triazole], is potentially ditopic. Nevertheless, L is shown herein to exclusively form mononuclear iron(II) complexes, [Fe(L)(NCE)]·solvent, in the presence of coordinating NCE anions (E = S or Se). Specifically, a new family of 10 mononuclear complexes, in which L binds in a monotopic bidentate manner, has been made: two solvent-free complexes, [Fe(L)(NCS)] (1) and [Fe(L)(NCSe)] (2); six solvatomorphs, 1·4CHCN, 2·4CHCN, 1·2.25CHCN, 2·3CHCN, 2·tetrahydrofuran, and 2·CHCl; and a pair of desolvated polymorphs, 1' and 2'. Seven of them are spin crossover-active, the exceptions being 1, 2, and 2'. This is confirmed by single-crystal X-ray diffraction (XRD) for 1, 2, 1·4CHCN, and 2·4CHCN and is consistent with variable-temperature optical microscopy observations on single crystals of 1·4CHCN and 2·4CHCN and on samples of 1' and 2'. Powder XRD, thermogravimetric analysis, and solid-state magnetometry reveal that desolvated 1' and 2' are capable of absorbing and desorbing a range of volatile guests: CHCN in both cases and also tetrahydrofuran and CHCl in the case of 2'.
基于哒嗪 - 吡啶三唑的大鼠配体L [4-(4 - 甲基苯基)-3-(3 - 哒嗪基)-5-(2 - 吡啶基)-1,2,4 - 三唑] 可能是双齿配体。然而，本文表明在存在配位的NCE阴离子（E = S或Se）的情况下，L仅形成单核铁（II）配合物[Fe(L)(NCE)]·溶剂。具体而言，已制备了一个由10种单核配合物组成的新家族，其中L以单齿双齿方式结合：两种无溶剂配合物，[Fe(L)(NCS)] (1) 和[Fe(L)(NCSe)] (2)；六种溶剂变体，1·4CHCN、2·4CHCN、1·2.25CHCN、2·3CHCN、2·四氢呋喃和2·CHCl；以及一对去溶剂化多晶型物，1'和2'。其中七种具有自旋交叉活性，例外的是1、2和2'。通过对1、2、1·4CHCN和2·4CHCN进行单晶X射线衍射（XRD）证实了这一点，并且这与对1·4CHCN和2·4CHCN单晶以及1'和2'样品进行的变温光学显微镜观察结果一致。粉末XRD、热重分析和固态磁学测量表明，去溶剂化的1'和2'能够吸收和解吸一系列挥发性客体：两种情况下均有CHCN，对于2'还有四氢呋喃和CHCl。
