Publikation: Oligomeric ferrocene rings
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2016
Autor:innen
Inkpen, Michael S.
Scheerer, Stefan
Linseis, Michael
White, Andrew J.P.
Winter, Rainer F.
Albrecht, Tim
Long, Nicholas J.
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Nature Chemistry. 2016, 8(9), pp. 825-830. ISSN 1755-4330. eISSN 1755-4349. Available under: doi: 10.1038/NCHEM.2553
Zusammenfassung
Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1′-disubstituted ferrocene units (cyclo[n], n = 5–7, 9). Due to the close proximity and connectivity of centres (covalent Cp–Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e– waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼107 s−1), these molecules can be considered as uniformly charged nanorings (diameter ∼1–2 nm).
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INKPEN, Michael S., Stefan SCHEERER, Michael LINSEIS, Andrew J.P. WHITE, Rainer F. WINTER, Tim ALBRECHT, Nicholas J. LONG, 2016. Oligomeric ferrocene rings. In: Nature Chemistry. 2016, 8(9), pp. 825-830. ISSN 1755-4330. eISSN 1755-4349. Available under: doi: 10.1038/NCHEM.2553BibTex
@article{Inkpen2016-09Oligo-34599,
year={2016},
doi={10.1038/NCHEM.2553},
title={Oligomeric ferrocene rings},
number={9},
volume={8},
issn={1755-4330},
journal={Nature Chemistry},
pages={825--830},
author={Inkpen, Michael S. and Scheerer, Stefan and Linseis, Michael and White, Andrew J.P. and Winter, Rainer F. and Albrecht, Tim and Long, Nicholas J.}
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<dcterms:abstract xml:lang="eng">Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1′-disubstituted ferrocene units (cyclo[n], n = 5–7, 9). Due to the close proximity and connectivity of centres (covalent Cp–Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e<sup>–</sup> waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼10<sup>7</sup> s<sup>−1</sup>), these molecules can be considered as uniformly charged nanorings (diameter ∼1–2 nm).</dcterms:abstract>
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