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Trialkyltetrathiafulvalene-sigma-tetracyanoanthraquinodimethane (R3TTF-sigma-TCNAQ) diads: Synthesis, intramolecular charge- transfer properties, and X-ray crystal structure

Perepichka, D.F.; Bryce, M.R.; Batsanov, A.S.; Howard, J.A.K.; Cuello, A.O.; Gray, M.; Rotello, V.M.

Authors

D.F. Perepichka

A.O. Cuello

M. Gray

V.M. Rotello



Abstract

We report the use of the electron-donating 4,5-dipentyl-4'- methyl-TTF (TTF = tetrathiafulvalene) moiety in combination with the electron acceptor 11,11,12,12- tetracyanoanthraquinodimethane (TCNAQ) unit in the novel D- sigma -A diad molecules 11, 17, and 18. These compounds display a weak, broad, low-energy intramolecular charge-transfer (ICT) band in the W-vis spectra (lambda (max) 430-450 nm). Cyclic voltammetric studies show two reversible one-electron oxidation processes for the R3TTF moiety, and a reversible two-electron reduction process for the TCNAQ moiety. The electron affinity of TCNAQ is significantly enhanced by the electron-withdrawing sulfonamide and sulfonic ester groups (compounds 17 and 18, respectively). Simultaneous electrochemistry and EPR (SEEPR) experiments show no significant intramolecular interaction between the R3TTF and TCNAQ moieties in compounds 11 and 18. X- ray crystallographic data are presented for 5, 11, and 20. The structure of 5 reveals hydrogen-bonded dimers. In molecule 11 the bond lengths and conformations of both donor and acceptor moieties are typical for neutral species. Compound 20 is an unusual calcium complex of TCNAQ derivative obtained by dicyanomethylation of anthraquinone-2-carboxylic acid.

Citation

Perepichka, D., Bryce, M., Batsanov, A., Howard, J., Cuello, A., Gray, M., & Rotello, V. (2001). Trialkyltetrathiafulvalene-sigma-tetracyanoanthraquinodimethane (R3TTF-sigma-TCNAQ) diads: Synthesis, intramolecular charge- transfer properties, and X-ray crystal structure. Journal of Organic Chemistry, 66(13), 4517-4524

Journal Article Type Article
Publication Date 2001-06
Journal Journal of Organic Chemistry
Print ISSN 0022-3263
Electronic ISSN 1520-6904
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 66
Issue 13
Pages 4517-4524
Public URL https://durham-repository.worktribe.com/output/1556947
Publisher URL <Go to ISI>://000169536700008