Ionic liquids with transition metal complex anions - magnetic ionic liquids

含过渡金属络合阴离子的离子液体-磁性离子液体

• 批准号: 29227441
• 负责人: Professor Dr. Martin Köckerling
• 金额: --
• 依托单位: Festkörperchemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2006
• 资助国家: 德国
• 起止时间: 2005-12-31 至 2011-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/29227441?language=en
• 关键词: Ionic; liquids; transition; metal; complex

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).

本研究拨款申请的主题是离子液体的合成和仔细表征，离子液体含有具有高自旋顺磁性构型的单阴离子过渡金属配合物。重点是这种新型离子液体的成员，其中电子以铁磁性有序自旋，这样这些材料对外部磁场有反应：磁性离子液体。为了达到更好地理解离子液体的目的，一般程序将是1)用顺磁性过渡金属阴离子合成大多数新的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。首先对目前已知的三种氯铁酸盐离子液体（emim）[FeIIICl4]、（emim）2[FIICI4]和（emim）4[FeIICI4][FeIIICl4]2进行研究，其中emim 1是唯一确定的磁性离子液体。后两个样品目前缺少磁性数据，前两个样品缺少晶体结构和理化数据，这些数据都将在本项目启动期内进行测量。在对氯铁酸盐进行这些研究之后，主要任务是合成一系列含有单核过渡金属络合物阴离子的高自旋顺磁性、带-1电荷的离子液体并对其进行彻底的表征。候选材料的选择侧重于[MLIxLIIy]（0或1¿）类型的杂电性配合物，其中含有阴离子（即卤代盐、硫氰酸盐、氰酸盐等）和中性（即胺、醇、水等）配体。为了得到离子液体，中性络合物将与有机卤化物RX （R = 1,3-二烷基咪唑、n -烷基吡啶、四烷基铵或磷，X = Cl、Br或i）熔合，这些含有已经存在的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都将进行彻底的物理化学表征，当然包括与温度相关的磁测量。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。拟议的研究具有很强的跨学科特征，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，理论计算和模拟将与R. Ludwig教授（罗斯托克大学）一起完成，磁测量将与R. Pöttgen教授（德国<s:1> nster大学）一起完成。