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. American Chemical Society (ACS). 2020, 39(17), pp. 3275-3289. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.0c00486
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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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ISO 690CASPER, 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). 2020, 39(17), pp. 3275-3289. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.0c00486
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@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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    <dcterms:abstract xml:lang="eng">We report on seven 4-ferrocenylphenyl-substituted tritylium dyes Fc-C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;-C&lt;sup&gt;+&lt;/sup&gt;Ar&lt;sub&gt;2&lt;/sub&gt; 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&lt;sup&gt;+&lt;/sup&gt;Ar&lt;sub&gt;2&lt;/sub&gt; 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.</dcterms:abstract>
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