Publikation: Synthesis, Spectroelectrochemistry and Electronic Structure Calculations of 4-(2-Ferrocenylvinyl)-[2.2]-paracyclophane and 4,12-di-(2-Ferrocenylvinyl)-[2.2]-paracyclophane
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Journal of Organometallic Chemistry. 2012, 717, pp. 14-22. ISSN 0022-328X. eISSN 0022-328X. Available under: doi: 10.1016/j.jorganchem.2012.07.020
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Abstract: 4,12-di-(2-ferrocenylvinyl)-[2.2]-paracyclophane 2 has been prepared and investigated with respect to its electrochemical and UV/Vis/NIR spectroelectrochemical properties. Cyclic and square wave voltammetric measurements show two consecutive one-electron oxidations with a moderate redox splitting of 112(±3) mV for the individual Fc/Fc+ couples. In spite of this redox splitting, radical cation 2•+ is a class I mixed-valent system with no detectable electronic coupling between the individual redox sites as is shown by the comparison of the Vis/NIR spectra of 2•+, 22+ and the radical cation of 4-(2-ferrocenylvinyl)-[2.2]-paracyclophane, 4•+. The NIR bands observed for the oxidized forms have been assigned as ferrocene-based d-d transitions by quantum chemical calculations.
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MÜCKE, Philipp, Rainer F. WINTER, Igor NOVAK, Konrad KOWALSKI, 2012. Synthesis, Spectroelectrochemistry and Electronic Structure Calculations of 4-(2-Ferrocenylvinyl)-[2.2]-paracyclophane and 4,12-di-(2-Ferrocenylvinyl)-[2.2]-paracyclophane. In: Journal of Organometallic Chemistry. 2012, 717, pp. 14-22. ISSN 0022-328X. eISSN 0022-328X. Available under: doi: 10.1016/j.jorganchem.2012.07.020BibTex
@article{Mucke2012Synth-20694,
year={2012},
doi={10.1016/j.jorganchem.2012.07.020},
title={Synthesis, Spectroelectrochemistry and Electronic Structure Calculations of 4-(2-Ferrocenylvinyl)-[2.2]-paracyclophane and 4,12-di-(2-Ferrocenylvinyl)-[2.2]-paracyclophane},
volume={717},
issn={0022-328X},
journal={Journal of Organometallic Chemistry},
pages={14--22},
author={Mücke, Philipp and Winter, Rainer F. and Novak, Igor and Kowalski, Konrad}
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<dcterms:abstract xml:lang="eng">Abstract: 4,12-di-(2-ferrocenylvinyl)-[2.2]-paracyclophane 2 has been prepared and investigated with respect to its electrochemical and UV/Vis/NIR spectroelectrochemical properties. Cyclic and square wave voltammetric measurements show two consecutive one-electron oxidations with a moderate redox splitting of 112(±3) mV for the individual Fc/Fc+ couples. In spite of this redox splitting, radical cation 2•+ is a class I mixed-valent system with no detectable electronic coupling between the individual redox sites as is shown by the comparison of the Vis/NIR spectra of 2•+, 22+ and the radical cation of 4-(2-ferrocenylvinyl)-[2.2]-paracyclophane, 4•+. The NIR bands observed for the oxidized forms have been assigned as ferrocene-based d-d transitions by quantum chemical calculations.</dcterms:abstract>
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