Publikation: Tailoring Valence Tautomerism using Redox Potentials : Studies on Ferrocene‐Based Triarylmethylium Dyes With Electron‐Poor Fluorenylium and Thioxanthylium Acceptors
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Three new electrochromic ferrocenyl triarylmethylium dyes with fluorenylium ( 1a + , 1b + ) or thioxanthylium ( 1c + ) residues were selected in order to keep the intrinsic differences of redox potentials for ferrocene oxidation and triarylmethylium reduction small and to trigger valence tautomerism. UV/Vis/NIR and quantitative EPR spectroscopy identified paramagnetic diradical isomers 1a +•• ‐1c +•• alongside diamagnetic forms 1a + ‐1c + , which renders these complexes magnetochemical switches. The diradical forms 1a +•• ‐1c +•• as well as the one‐electron reduced triarylmethyl forms of the complexes were found to dimerize in fluid solution. For radical 1a • , dimerization occurs on the timescale of cyclic voltammetry, which allowed us to determine the kinetics and equilibrium constant for this process by digital simulation. Mößbauer spectroscopy indicated that 1a + and 1b + retain VT even in the solid state. UV/Vis/NIR spectroelectrochemistry revealed the polyelectrochromic behaviour of these complexes by establishing distinctly different electronic absorption profiles of the corresponding oxidized and reduced form s.
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WINTER, Rainer F., Larissa A. CASPER, Michael LINSEIS, Serhiy DEMESHKO, Mykhailo AZARKH, Malte DRESCHER, 2021. Tailoring Valence Tautomerism using Redox Potentials : Studies on Ferrocene‐Based Triarylmethylium Dyes With Electron‐Poor Fluorenylium and Thioxanthylium Acceptors. In: Chemistry – A European Journal. Wiley. 2021, 27(42), pp. 10854-10868. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.202101032BibTex
@article{Winter2021-07-26Tailo-53491, year={2021}, doi={10.1002/chem.202101032}, title={Tailoring Valence Tautomerism using Redox Potentials : Studies on Ferrocene‐Based Triarylmethylium Dyes With Electron‐Poor Fluorenylium and Thioxanthylium Acceptors}, number={42}, volume={27}, issn={0947-6539}, journal={Chemistry – A European Journal}, pages={10854--10868}, author={Winter, Rainer F. and Casper, Larissa A. and Linseis, Michael and Demeshko, Serhiy and Azarkh, Mykhailo and Drescher, Malte} }
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