Boudalis Athanassios K, Rogez Guillaume, Heinrich Benoît, Raptis Raphael G, Turek Philippe
Department of Chemistry and Biochemistry and the Biomolecular Sciences Institute, Florida International University, Miami, FL 33199, USA and Institut de Chimie de Strasbourg (UMR 7177, CNRS-Unistra), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, F-67081 Strasbourg, France.
Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504, F-67000 Strasbourg, France.
Dalton Trans. 2017 Sep 28;46(36):12263-12273. doi: 10.1039/c7dt02472j. Epub 2017 Sep 7.
Complexes (bmim)[Cu(μ-Cl)(μ-pz)Cl] (1), (bmim)[Cu(μ-OH)(μ-pz)Cl] (2) and (bmim)[Cu(μ-OH)(μ-Cl)(μ-pz)Cl] (3) were synthesized (bmim = 1-butyl-3-methylimidazolium, pz = pyrazolato anion). Dianionic complexes 1 and 3 were obtained as crystalline solids, whereas the monoanionic complex 2 was obtained as a viscous paste. Magnetic susceptibility and X-band EPR studies revealed intramolecular ferromagnetic interactions for 1 with small magnetoanisotropy in its ground state (D∼ 10 cm) and intramolecular antiferromagnetic interactions for 2 and 3 (-285 and -98 cm average J, respectively) with important magnetic anisotropy in their ground states stemming from a combination of low magnetic symmetry and antisymmetric exchange interactions. Thermal studies revealed a clear melting point of 140 °C for 1, which is lower than that of its PPN and BuN analogues (1PPN and 1BuN, respectively, PPN = bis(triphenylphosphine)iminium). Upon cooling, 1 remains molten down to 70 °C. Mixtures of the salts 1, 1PPN and 1BuN, exhibited modified melting behaviours, with the mixtures exhibiting lower melting points than those of either of their pure components.
合成了配合物(bmim)[Cu(μ-Cl)(μ-pz)Cl] (1)、(bmim)[Cu(μ-OH)(μ-pz)Cl] (2)和(bmim)[Cu(μ-OH)(μ-Cl)(μ-pz)Cl] (3)（bmim = 1-丁基-3-甲基咪唑鎓，pz = 吡唑阴离子）。二阴离子配合物1和3以结晶固体形式获得，而单阴离子配合物2以粘性糊状物形式获得。磁化率和X波段电子顺磁共振研究表明，1在基态具有分子内铁磁相互作用且磁各向异性较小（D ∼ 10 cm），2和3具有分子内反铁磁相互作用（平均J分别为-285和-98 cm），其基态具有重要的磁各向异性，这源于低磁对称性和反对称交换相互作用的结合。热学研究表明，1的熔点为140 °C，低于其PPN和BuN类似物（分别为1PPN和1BuN，PPN = 双（三苯基膦）亚胺鎓）。冷却时，1在降至70 °C时仍保持熔融状态。盐1、1PPN和1BuN的混合物表现出改变的熔化行为，混合物的熔点低于其任何一种纯组分的熔点。
