Ionic liquids with transition metal complex anions - magnetic ionic liquids

本研究资助申请的主题是离子液体的合成和仔细表征，其中含有表现出高自旋顺磁配置的单阴离子过渡金属络合物。重点是这类新的离子液体的成员，其中电子自旋顺序铁磁性，使这些材料响应外部磁场：磁性离子液体。达到有助于更好地理解离子液体的目标的一般程序将是1）合成大多数具有顺磁性过渡金属阴离子的新IL，2）测量物理化学性质（特别是磁性），以及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。本文首先对三种已知的铁氯酸盐基离子液体（emim）[FeIIICl_4]、（emim）_2 [FIICl_4]和（emim）_4 [FeIICl_4][FeIIICl_4]_2进行了研究，其中第一种是目前唯一确定的磁性离子液体。最后两个至今没有磁性数据，前两个的晶体结构以及物理化学数据，这些数据都将在项目启动期间进行测量。在对氯高铁酸盐进行这些研究之后，主要任务是合成和彻底表征一系列离子液体，其含有单核过渡金属络合物阴离子，其具有高自旋顺磁性并且携带-1电荷。候选材料的选择集中在含有阴离子（即卤代、硫氰基、氰基等）的[MLIxLIIy]（0或1 <$）型杂配配合物上。以及中性（即胺、醇、H2O等）配体。为了得到离子液体，将中性络合物与有机卤化物RX稠合，其中R = 1，3-二烷基咪唑鎓、N-烷基吡啶鎓、四烷基铵或磷鎓，X = Cl、Br或I。那些已经含有单阴离子的络合物通过复分解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将进行彻底的物理化学表征，当然包括温度依赖的磁性测量。这将导致与理论（计划是量子力学和Car-Parinello分子动力学计算）相结合，以更深入地了解离子液体的分子部分相互作用的方式。该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.伯克尔（罗斯托克大学），理论计算和模拟教授，博士R。Ludwig教授（罗斯托克大学）和R. Pöttgen（明斯特大学）。

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).