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By P. P. Ewald

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70 °C and 0 °C with a minimum located at ca. -50 °C to -60 °C. It is proposed that the difference in melting behavior is due to the transition metal cations incorporated in the cluster shells: compounds 6, 8 and 9 feature metal cations which are redox-inert under the given reaction conditions (CuII, NiII, FeIII, respectively). In contrast, compounds 7, 10 and 12 contain redox-active metals (MnII, CoII, CrIII) and it is proposed that under the given conditions, partial oxidation results in the in-situ generation of “intrinsic” impurities which contribute to the unexpected melting behavior.

The synthesis of new POM-ILs is supposed to be achieved using sterically demanding cations like tetraalkylammonium, tetraalkylphosphonium or imidazolium ions featuring long alkyl chains. Tunability of the ILs properties is further realized by alternation of the heteroatoms and incorporation of different d-elements into the lacunary site(s) of the mono- or polyvacant cluster anions. Basic characterization of the obtained products is carried out by elemental analysis (EA), infrared spectroscopy (IR) and UV-Vis spectroscopy.

1007/978-3-658-08796-8_2, © Springer Fachmedien Wiesbaden 2015 19 Figure 11 Molecular model for a true POM-IL (left) vs. a POM dissolved in IL (right). The POM-IL exhibits a much higher cluster density and has less different electrostatic interactions. In a POM-IL only interactions among POMs (blue polyhedra with templating heteroelement in pink) and their charge balancing cations (purple tetrahedrals) are possible, whereas for POMs dissolved in a ionic liquid additional interactions with the ionic liquids cations (black balls) and anions (grey balls) occur.

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