Ionic liquids with transition metal complex anions - magnetic ionic liquids

• Antragsteller: Professor Dr. Martin Köckerling
• Fachliche Zuordnung: Anorganische Molekülchemie - Synthese, Charakterisierung
• Förderung: Förderung von 2006 bis 2012
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 29227441

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).

• DFG-Verfahren: Schwerpunktprogramme
• Teilprojekt zu: SPP 1191: Ionische Flüssigkeiten