Electron acceptors of the fluorene series. Part 13. 9-(5- Nitrofuran-2-ylidene)- and 9-(5-nitro-2-thienylidene)-2,4,5,7- tetranitrofluorenes: novel pi-extended electron acceptors. Synthesis, cyclic voltammetry and X-ray crystal structures for the acceptor

Perepichka, I.F.; Perepichka, D.F.; Lyubchik, S.B.; Bryce, M.R.; Batsanov, A.S.; Howard, J.A.K.

Abstract

Two novel polynitrofluorene acceptors pi -extended with 5- nitrofuran and 5-nitrothiophene moieties (2 and 3); have been synthesised. Cyclic voltammetry experiments show single electron reduction peaks at ca. -0.66-0.67 V (vs. Fc/Fc(+)); however, this process (probably due to substantial changes in geometry of reduced species) is electrochemically irreversible and re-oxidation of the derived radical anions is observed at +0.05 and -0.04 V, for 2 and 3, respectively. Electronic absorption spectroscopy confirms charge transfer complexation of the studied acceptor with 4,5-dimethyltetrathiafulvalene (Me2TTF) in solution. The X-ray crystal structure of the 1 : 1 charge transfer complex (CTC) of acceptor 2 with Me2TTF shows mixed A . . .D . . .A . . .D stacking, and its comparison with the structure of the acceptor itself indicates a neutral ground state of this CTC. Theoretical HF/6-31 G(d) calculations for the acceptor 2 and its radical anion and dianion states are in agreement with this conclusion. Intramolecular hydrogen bonding in 2 between the oxygen of the furan ring and C(8)-H hydrogen of the fluorene moiety is observed in both solution (H-1 NMR) and solid state (X-ray) and also supported by theoretical calculations.

Citation

Perepichka, I., Perepichka, D., Lyubchik, S., Bryce, M., Batsanov, A., & Howard, J. (2001). Electron acceptors of the fluorene series. Part 13. 9-(5- Nitrofuran-2-ylidene)- and 9-(5-nitro-2-thienylidene)-2,4,5,7- tetranitrofluorenes: novel pi-extended electron acceptors. Synthesis, cyclic voltammetry and X-ray crystal structures for the acceptor. Journal of the Chemical Society-Perkin Transactions 2, 2001(9), 1546-1551

• Journal Article Type: Article
• Publication Date: 2001-09
• Journal: Journal of the Chemical Society, Perkin Transactions 2
• Print ISSN: 1470-1820
• Electronic ISSN: 2050-8247
• Peer Reviewed: Peer Reviewed
• Volume: 2001
• Issue: 9
• Pages: 1546-1551
• Public URL: https://durham-repository.worktribe.com/output/1580344
• Publisher URL: <Go to ISI>://000171185600017