Ferrocenyl‐Pyrenes, Ferrocenyl‐9,10‐Phenanthrenediones, and Ferrocenyl‐9,10‐Dimethoxyphenanthrenes: Charge‐Transfer Studies and SWCNT Functionalization
2019; Wiley; Volume: 26; Issue: 12 Linguagem: Inglês
10.1002/chem.201904450
ISSN1521-3765
AutoresAndrea Preuß, Sebastian Notz, Eduard Kovalski, Marcus Korb, Thomas Blaudeck, Xiao Hu, Jörg Schuster, Dominique Miesel, Tobias Rüffer, Alexander Hildebrandt, Katja Schreiter, Stefan Spange, Stefan E. Schulz, Heinrich Lang,
Tópico(s)Conducting polymers and applications
ResumoAbstract The synthesis of 1‐Fc‐ ( 3 ), 1‐Br‐6‐Fc‐ ( 5 a ), 2‐Br‐7‐Fc‐ ( 7 a ), 1,6‐Fc 2 ‐ ( 5 b ), 2,7‐Fc 2 ‐pyrene ( 7 b ), 3,6‐Fc 2 ‐9,10‐phenanthrenedione ( 10 ), and 3,6‐Fc 2 ‐9,10‐dimethoxyphenanthrene ( 12 ; Fc=Fe(η 5 ‐C 5 H 4 )(η 5 ‐C 5 H 5 )) 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 Fe II /Fe III 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.
Referência(s)