Adding to the versatile class of ionic liquids, we report the detailed structure and property analysis of a new class of asymmetrically substituted imidazolium salts, offering interesting thermal characteristics, such as liquid crystalline behavior, polymorphism or glass transitions. A scalable general synthetic procedure for N-polyaryl-N'-alkyl-functionalized imidazolium salts with para-substituted linker (L) moieties at the aryl chain, namely [LPhm ImH R]+ (L=Br, CN, SMe, CO2 Et, OH; m=2, 3; R=C12 , PEGn ; n=2, 3, 4), was developed. These imidazolium salts were studied by single-crystal X-ray diffraction (SC-XRD), NMR spectroscopy and thermochemical methods (DSC, TGA). Furthermore, these imidazolium salts were used as N-heterocyclic carbene (NHC) ligand precursors for mononuclear, first-row transition metal complexes (MnII , FeII , CoII , NiII , ZnII , CuI , AgI , AuI ) and for the dinuclear Ti-supported Fe-NHC complex [(OPy)2 Ti(OPh2 ImC12 )2 (FeI2 )] (OPy=pyridin-2-ylmethanolate). The complexes were studied concerning their structural and magnetic behavior via multi-nuclear NMR spectroscopy, SC-XRD analyses, variable temperature and field-dependent (VT-VF) SQUID magnetization methods, X-band EPR spectroscopy and, where appropriate, zero-field 57 Fe Mössbauer spectroscopy.
Keywords: carbene ligands; electronic structure; ionic liquids; solid-state structure; thermal properties.
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