The First Tetrathiafulvalene-σ-Polynitrofluorene Diads: Low HOMO-LUMO Gap, Amphoteric Redox Behavior, and Charge Transfer Properties

Organic Letters

Volumn 3, Issue 10, 2001, Pages 1431-1434

  Perepichka, Dmitrii F ^a   Bryce, Martin R ^a   McInnes, Eric J L ^b   Zhao, Jing P ^b  

^a DURHAM UNIVERSITY   (United Kingdom)

^b UNIVERSITY OF MANCHESTER   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001531890     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015581r     Document Type: Article

References (26)

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2. Aviram, A.; Ratner, M. Chem. Phys. Lett. 1974, 29, 277. For recent discussions of this proposal, see: Metzger, R. M. J. Mater. Chem. 1999, 9, 2027.
3. (a) Bryce, M. R. Adv. Mater. 1999, 11, 11 and references therein.
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14. Perepichka, I. F.; Popov, A. F.; Orekhova, T. V.; Bryce, M. R.; Andrievskii, A. M.; Batsanov, A. S.; Heaton, J.; Howard, J. A. K.; Sokolov, N. I. J. Org. Chem. 2000, 65, 3053.
15. 4-Methyl-4′,5′-dipentylTTF was synthesized by analogy with trimethylTTF: Moore, A. J.; Bryce, M. R.; Batsanov, A. S.; Cole, J. C.; Howard, J. A. K. Synthesis 1995, 675. The pentyl chains increased the solubility of 5 and 6 in organic solvents.
16. -1 2928, 2203, 1742, 1543, 1340, 1133.
17. Ribera, E.; Rovira, C.; Veciana, J.; Tarrés, J.; Canadell, E.; Rousseau, R.; Molins, E.; Mas, M.; Schoeffel, J.-P.; Pouget, J.-P.; Morgado, J.; Henriques, R. T.; Almeida, M. Chem. Eur. J. 1999, 5, 2025.
18. (a) A possible explanation for the quenching of the radical anion signal could be the formation of dimers by the fluorene radical anion moieties (the formation of dimers of radical anions of a similar acceptor, TCNQ, is well-known: Boyd, R. H.; Phillips, W. D. J. Phys. Chem. 1965, 43, 2927).
19. (b) In every EPR experiment the solutions were thoroughly degassed.
20. •- couple: Chappel, J. S.; Bloch, A. N.; Bryden, W. A.; Maxfield, M., Poehler, T. O.; Cowan, D. O. J. Am. Chem. Soc. 1981, 103, 2442.
21. + shows 0.50 V in these conditions.
22. HOMO-LUMO gap of 0.3 eV is most unusual for monomeric organic compounds, but well-known for rare-earth organometallic compounds: Jiang, J.; Liu, W.; Poon, K.-W.; Du, D.; Arnold, D. P.; Ng, D. K. P. Eur. J. Inorg. Chem. 2000, 205, and references therein.
23. (a) This is also supported by geometry optimization of 6 with the semiempirical PM3 method showing that "extended" and folded "head-to-tail" conformations, where intramolecular π-π charge transfer can take place, are very close in energy.
24. ICT (1 eV) and the electrochemically determined HOMO-LUMO gap (0.3 eV) could be explained by the fact that whereas the ICT transition occurs solely from the intramolecularly complexed state of the molecule (where donor-acceptor interaction increases the gap), CV characterizes the "uncomplexed" or equilibrium state.
25. (a) Mortimer, R. J. Chem. Soc. Rev. 1997, 26, 147.
26. (b) Hünig, S.; Kemmer, M.; Wenner, H.; Perepichka, I. F.; Bäuerle, P.; Emge, A.; Gescheid, G. Chem. Eur. J. 1999, 5, 1969.