4-Ferrocenylphenyl-Substituted Tritylium Dyes with Open and Interlinked C+Ar2 Entities : Redox Behavior, Electrochromism, and a Quantitative Study of the Dimerization of Their Neutral Radicals
4-Ferrocenylphenyl-Substituted Tritylium Dyes with Open and Interlinked C+Ar2 Entities : Redox Behavior, Electrochromism, and a Quantitative Study of the Dimerization of Their Neutral Radicals
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Organometallics ; 39 (2020), 17. - pp. 3275-3289. - American Chemical Society (ACS). - ISSN 0276-7333. - eISSN 1520-6041
Abstract
We report on seven 4-ferrocenylphenyl-substituted tritylium dyes Fc-C6H4-C+Ar2 with either unlinked or interlinked aryl residues Ar, including congeners with six-membered (thio)xanthylium and seven-membered (dihydro)dibenzo[a,d]cycloheptatrienylium motifs. All complexes are intensely colored and show more or less intense absorption bands owing to charge transfer from the 4-ferrocenylphenyl donor to the C+Ar2 acceptor unit as well as reversible electrochromism upon reduction and oxidation. The spectral profiles and redox potentials depend on whether or not the methylium center is incorporated into a 14-π-electron arene system. T-dependent EPR spectroscopy indicates that their one-electron-reduced neutral radicals dimerize. The ensuing monomer–dimer equilibria were studied by quantitative spin-counting methods, which revealed an unexpectedly large extent of 85.0–99.6% of dimerization.
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CASPER, Larissa A., Lukas WURSTHORN, Marcel GEPPERT, Patrick ROSER, Michael LINSEIS, Malte DRESCHER, Rainer F. WINTER, 2020. 4-Ferrocenylphenyl-Substituted Tritylium Dyes with Open and Interlinked C+Ar2 Entities : Redox Behavior, Electrochromism, and a Quantitative Study of the Dimerization of Their Neutral Radicals. In: Organometallics. American Chemical Society (ACS). 39(17), pp. 3275-3289. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.0c00486BibTex
@article{Casper2020-09-144Ferr-51322, year={2020}, doi={10.1021/acs.organomet.0c00486}, title={4-Ferrocenylphenyl-Substituted Tritylium Dyes with Open and Interlinked C<sup>+</sup>Ar<sub>2 </sub> Entities : Redox Behavior, Electrochromism, and a Quantitative Study of the Dimerization of Their Neutral Radicals}, number={17}, volume={39}, issn={0276-7333}, journal={Organometallics}, pages={3275--3289}, author={Casper, Larissa A. and Wursthorn, Lukas and Geppert, Marcel and Roser, Patrick and Linseis, Michael and Drescher, Malte and Winter, Rainer F.} }
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