Ionic liquids with transition metal complex anions - magnetic ionic liquids

这项研究资助申请的主题是离子液体的合成和仔细表征，其中包含具有高自旋顺磁构型的单阴离子过渡金属络合物。重点放在这类新的离子液体上，其中电子的自旋是铁磁性的，这样这些材料就可以响应外部磁场：磁性离子液体。达到更好地理解离子液体的目标的一般步骤将是1)用顺磁性过渡金属阴离子合成主要新的IL S，2)测量其物理化学性质(特别是磁性)，3)进行理论计算(量子力学和CAR-Parinello分子动力学模拟)，以提高对组成/结构-性质关系的理解。首先对目前已知的三种基于氯高铁酸盐的离子液体(EMIM)[FeIIICL4]，(EMIM)2[FIICI4]和(EMIM)4[FeIICI4][FeIIICL4]2进行了研究，其中第一种是唯一被鉴定的磁性离子液体。到目前为止，最后两个项目的磁性数据、前两个项目的晶体结构以及物理化学数据都丢失了，这些数据都将在该项目的启动期内进行测量。在这些关于氯高铁酸盐的研究之后，主要的任务是合成和彻底表征一系列离子液体，这些离子液体含有单核过渡金属络合阴离子，它们是高自旋顺磁性的，带有-1的电荷。候选材料的选择主要集中在含有阴离子(即卤代、硫氰基、氰基等)的[MLIxLIIy](0或1？)类型的异感络合物。以及中性(即胺、醇孔、水等)配基。为了得到离子液体，中性络合物将与R=1，3-二烷基咪唑、N-烷基吡啶、四烷基铵或膦以及X=Cl、Br1或I的有机卤化物RX熔合，这些已含有单阴离子的络合物通过歧化反应或离子交换转化为所需的离子液体。所有合成的离子液体都将经过彻底的物理化学表征，当然包括与温度相关的磁测量。这应该会导致结合理论(计划进行量子力学和CAR-Parinello分子动力学计算)来更深入地理解离子液体的分子部分相互作用的方式。拟议的研究具有很强的跨学科性质，物理化学表征将与A Heintz教授和E.Burkel教授(罗斯托克大学)一起完成，与R.Ludwig教授(罗斯托克大学)一起进行理论计算和模拟，并与R.Pöttgen教授(明斯特大学)一起进行磁测量。

Subject of this research grant application is the synthesis and careful characterization of Ionic Liquids, which contain monoanionic transition metal complexes exhibiting high-spin paramagnetic configurations. The emphasis is on those members of this new class of Ionic Liquids, wherein the electron spins order ferromagnetically, such that these materials respond on external magnetic fields: Magnetic Ionic Liquids.The general procedure to reach the goal of a contribution to a better understanding of Ionic Liquids will be 1) to synthesize mostly new IL s with paramagnetic transition metal anions, 2) to measure the physico-chemical properties (especially the magnetic properties), and 3) to perform theoretical calculations (quantum mechanical and Car-Parinello molecular dynamical simulations) to improve the understanding of composition/structure - property relations. First investigations will be done on the three so far known chloroferrate based Ionic Liquids, (emim)[FeIIICl4], (emim)2[FIICI4], and (emim)4[FeIICI4][FeIIICl4]2, of which the first one is the only identified magnetic ionic Liquid. Magnetic data are missing up to now for the last two ones, and crystal structures of the first two ones, as well as physico-chemical data, which all will be measured within the starting period of this project. Following these investigations on chloroferrates, the main task is the synthesis and thorough characterization of a series of Ionic Liquids, containing mononuclear transition metal complex anions, which are high-spin paramagnetic and carry a charge of -1. The selection of candidate materials focuses on heteroleptic complexes of the type [MLIxLIIy](0 or 1¿) containing anionic (i.e. halido, thiocyanido, cyanido, etc.) as well as neutral (i.e. amine, alcohole, H2O, etc.) ligands. To yield the Ionic Liquids the neutral complexes will be fused with organic halides RX with R = 1,3-dialkylimidazolium, N-alkylpyridinium, tetraalkylammonium- or phosphonium, and X = Cl, Br, or I. Those complexes, which contain already monoanions are transformed into the desired Ionic Liquids through metathesis reactions or ion exchange. All the synthesized Ionic Liquids will be subjected to a thorough physicochemical characterization including of course temperature dependent magnetic measurements. This should lead in combination with theoretical (planned are quantum mechanical and Car-Parinello molecular dynamics calculations) to a deeper understanding of the way the molecular parts of Ionic Liquids interact. The proposed research has strong interdisciplinary character, physico-chemical characterizations will be done together with Prof. Dr. A Heintz and Prof. Dr. E. Burkel (University of Rostock), theoretical calculations and simulations with Prof, Dr. R. Ludwig (University of Rostock), and the magnetic measurements with Prof, Dr. R. Pöttgen (University of Münster).