Trialkyltetrathiafulvalene-sigma-tetracyanoanthraquinodimethane [R(3)TTF-sigma-TCNAQ] diads: synthesis, intramolecular charge-transfer properties, and X-ray crystal structure

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

doi:10.1021/jo001576+

Trialkyltetrathiafulvalene-sigma-tetracyanoanthraquinodimethane [R(3)TTF-sigma-TCNAQ] diads: synthesis, intramolecular charge-transfer properties, and X-ray crystal structure

J Org Chem. 2001 Jun 29;66(13):4517-24. doi: 10.1021/jo001576+.

Authors

D F Perepichka¹, M R Bryce, A S Batsanov, J A Howard, A O Cuello, M Gray, V M Rotello

Affiliation

¹ Department of Chemistry, University of Durham, Durham DH1 3LE, U.K.

PMID: 11421770
DOI: 10.1021/jo001576+

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 UV-vis spectra (lambda(max) 430-450 nm). Cyclic voltammetric studies show two reversible one-electron oxidation processes for the R(3)TTF 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 R(3)TTF 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.