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Ferrocenyl-Pyrenes,Ferrocenyl-9,10-Phenanthrenediones,and Ferrocenyl-9,10-Dimethoxyphenanthrenes: Charge-Transfer Studies and SWCNT Functionalization |
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| Authors: | Andrea Preuß Sebastian Notz Eduard Kovalski Dr Marcus Korb Dr Thomas Blaudeck Dr Xiao Hu Dr Jörg Schuster Dr Dominique Miesel Dr Tobias Rüffer Dr Alexander Hildebrandt Dr Katja Schreiter Prof?Dr Stefan Spange Prof?Dr Stefan E Schulz Prof?Dr Heinrich Lang |
| Institution: | 1. Faculty of Natural Sciences, Institute of Chemistry, Inorganic Chemistry, Technische Universität Chemnitz, 09107 Chemnitz, Germany;2. Faculty of Natural Sciences, Institute of Chemistry, Inorganic Chemistry, Technische Universität Chemnitz, 09107 Chemnitz, Germany
Current address: Faculty of Science, School of Molecular Sciences, The University of Western Australia, Crawley, Perth, WA, 6009 Australia;3. Center for Microtechnologies (ZfM), Technische Universität Chemnitz, 09107 Chemnitz, Germany Fraunhofer Institute for Electronic Nano Systems (ENAS), Technologie-Campus 3, 09126 Chemnitz, Germany;4. Center for Microtechnologies (ZfM), Technische Universität Chemnitz, 09107 Chemnitz, Germany Fraunhofer Institute for Electronic Nano Systems (ENAS), Technologie-Campus 3, 09126 Chemnitz, Germany Center for Advancing Electronics Dresden (cfaed), 09107 Chemnitz, Germany;5. Faculty of Natural Sciences, Institute of Chemistry, Polymer Chemistry, Technische Universität Chemnitz, 09107 Chemnitz, Germany |
| Abstract: | The synthesis of 1-Fc- ( 3 ), 1-Br-6-Fc- ( 5 a ), 2-Br-7-Fc- ( 7 a ), 1,6-Fc2- ( 5 b ), 2,7-Fc2-pyrene ( 7 b ), 3,6-Fc2-9,10-phenanthrenedione ( 10 ), and 3,6-Fc2-9,10-dimethoxyphenanthrene ( 12 ; Fc=Fe(η5-C5H4)(η5-C5H5)) is discussed. Of these compounds, 10 and 12 form 1D or 2D coordination polymers in the solid state. (Spectro)Electrochemical studies confirmed reversible Fc/Fc+ redox events between ?130 and 160 mV. 1,6- and 2,7-Substitution in 5 a (E°′=?130 mV) and 7 a (E°′=50 mV) influences the redox potentials, whereas the ones of 5 b and 7 b (E°′=20 mV) are independent. Compounds 5 b , 7 b , 10 , and 12 show single Fc oxidation processes with redox splittings between 70 and 100 mV. UV/Vis/NIR spectroelectrochemistry confirmed a weak electron transfer between FeII/FeIII in mixed-valent 5 b ]+ and 12 ]+. DFT calculations showed that 5 b non-covalently interacts with the single-walled carbon nanotube (SWCNT) sidewalls as proven by, for example, disentangling experiments. In addition, CV studies of the as-obtained dispersions confirmed exohedral attachment of 5 b at the SWCNTs. |
| Keywords: | (spectro)electrochemistry density functional calculations ferrocene pyrene solid-state structures solvatochromism |