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Electron acceptors of the fluorene series. Part 12. 9- (Metalloceneylidene)nitrofluorene derivatives of Fc-NF, NF-Fc- NF, and NF-Rc-NF types, and the vinylogues Fc-pi-NF: synthesis, characterisation, intramolecular charge transfer, redox properties and X-

Perepichka, D.F.; Perepichka, I.F.; Popov, A.F.; Bryce, M.R.; Batsanov, A.S.; Chesney, A.; Howard, J.A.K.; Sokolov, N.I.

Authors

D.F. Perepichka

I.F. Perepichka

A.F. Popov

A. Chesney

N.I. Sokolov



Abstract

Reaction of ferrocenecarboxaldehyde 13 and its vinylogue, (E,E)-1-ferrocenyl-4-formyl-1,3-butadiene (16), with nitrofluorenes as CH-acids, results in push-pull compounds of the type Fc-pi -fluorene (8a-g, 12a-e). Similar reaction with bifunctional ferrocene and ruthenocene dicarboxaldehydes results, depending on the fluorene structure, in the products of mono- or di-condensation, OHC-Fc-CH=fluorene (11d,e) or fluorene=CH-Fc-CH=fluorene and fluorene=CH-Rc-CH=fluorene (9a- c, 10a-c). Intramolecular charge transfer (ICT) in compounds 8 results in lowering the rotation barrier around the CH=fluorene double bond and easy E-Z isomerisation in solution. Cyclic voltammetry (CV) experiments show a reversible single-electron oxidation of Fc-CH=fluorenes (8) yielding the cation and two reversible single-electron reduction waves yielding the radical anion and dianion (for 8a-e) which merge into one two-electron reduction wave for 8f-h. ICT was also manifested in the electron absorption spectra of 8-12, and energies of ICT (as well as reduction potentials in CV) were found to display excellent correlation (r greater than or equal to 0.99) with Hammett-type substituents constants (sigma (-)(p)) in the fluorene moiety. Compounds 8-12 show solvatochromism [8a: lambda (ICT) = 604.5 nm (acetonitrile), 622.5 nm (1,2- dichloroethane)], with, however, no quantitative regularities for 10 solvents of different polarity. Bathochromic shifts of 40-83 run. and an increase in the intensity of ICT bands were observed with lengthening of the pi -bridge between ferrocene and fluorene moieties (8 --> 12) whereas substitution of the ferrocene unit in 9 by the ruthenocene unit (10) resulted to a hypsochromic shift of ca. 100 nm due to decreasing donor ability of the latter metallocene fragment. Acceptor 8a was found to sensitise the photoconductivity of poly-N-(2,3- epoxypropyl)carbazole showing moderate holographic response of the materials. Molecular and crystal structures for ferrocene derivatives 8a, 8g, and 11d were determined by single-crystal X-ray diffraction. Tetranitro derivative 8a shows substantial distortion, caused by steric repulsion between the nitro groups in positions 4 and 5, which precludes the formation of stacks, and pairs of fluorene moieties contact face-to-face (interplanar distance 3.8 Angstrom). In di- and trinitro derivatives 8g and 11d the fluorene moieties are more planar and their crystal packing motifs are similar: fluorene moieties form good stacks, parallel to the x-axis in 8g and the y-axis in 11d, with interplanar separations between fluorene moieties of 3.35-3.36 Angstrom for 8g and alternate separations of 3.52 and 3.55 Angstrom for 11d. (C) 2001 Elsevier Science B.V. All rights reserved.

Citation

Perepichka, D., Perepichka, I., Popov, A., Bryce, M., Batsanov, A., Chesney, A., …Sokolov, N. (2001). Electron acceptors of the fluorene series. Part 12. 9- (Metalloceneylidene)nitrofluorene derivatives of Fc-NF, NF-Fc- NF, and NF-Rc-NF types, and the vinylogues Fc-pi-NF: synthesis, characterisation, intramolecular charge transfer, redox properties and X-. Journal of Organometallic Chemistry, 637, 445-462

Journal Article Type Article
Publication Date 2001-12
Journal Journal of Organometallic Chemistry
Print ISSN 0022-328X
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 637
Pages 445-462
Publisher URL <Go to ISI>://000172577800058