New functionalized tetrathiafulvalenes: X-ray crystal structures and physico-chemical properties of TTF-C(O)NMe2 and TTF-C(O)-O-C4H9: a joint experimental and theoretical study

A.S. Batsanov, M.R. Bryce, J.N. Heaton, A.J. Moore, P.J. Skabara, J.A.K. Howard, E. Ortí, P.M. Viruela, R. Viruela

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Abstract

The synthesis of the new mono- and di-functionalized tetrathiafulvalene (TTF) derivatives 4, 5 and 12-15 is reported. Compounds 4 and 5 have been studied in detail: their single crystal X-ray structures are reported and theoretical calculations at both semiempirical and ab initio levels have been performed. The TTF moiety in the crystal of 4 is folded, whereas in the crystal of 5 it is essentially planar. In the crystal structure of 4 the molecules related via an inversion centre form close dimers which pack in a severely distorted kappa-arrangement. Molecules of 5 assemble into uniform stacks with TTF moieties overlapping the side chains of adjacent molecules. Calculated geometries are in good agreement with the X-ray data, and the distortion from planarity in the crystal of 4 can be explained by nonbonding interactions between the amide substituent and the TTF rings of adjacent molecules. Evidence for intramolecular charge-transfer from the TTF ring to the electron-withdrawing amide and ester substituents of 4 and 5, respectively, is provided by UV-VIS spectroscopy in solution, analysis of the bond lengths in the crystal structure, and by theoretical calculations.
LanguageEnglish
Pages1689-1696
Number of pages7
JournalJournal of Materials Chemistry
Volume5
Issue number10
DOIs
Publication statusPublished - 1995

Fingerprint

Chemical properties
Crystal structure
X rays
Molecules
Amides
Crystals
Bond length
Ultraviolet spectroscopy
Dimers
Charge transfer
Esters
Single crystals
Derivatives
Geometry
tetrathiafulvalene
Electrons

Keywords

  • semiempirical methods
  • kappa-phase
  • parameters
  • optimization
  • derivatives
  • molecules
  • sulfur
  • states
  • MNDO
  • TTF

Cite this

Batsanov, A.S. ; Bryce, M.R. ; Heaton, J.N. ; Moore, A.J. ; Skabara, P.J. ; Howard, J.A.K. ; Ortí, E. ; Viruela, P.M. ; Viruela, R. / New functionalized tetrathiafulvalenes: X-ray crystal structures and physico-chemical properties of TTF-C(O)NMe2 and TTF-C(O)-O-C4H9: a joint experimental and theoretical study. In: Journal of Materials Chemistry. 1995 ; Vol. 5, No. 10. pp. 1689-1696.
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abstract = "The synthesis of the new mono- and di-functionalized tetrathiafulvalene (TTF) derivatives 4, 5 and 12-15 is reported. Compounds 4 and 5 have been studied in detail: their single crystal X-ray structures are reported and theoretical calculations at both semiempirical and ab initio levels have been performed. The TTF moiety in the crystal of 4 is folded, whereas in the crystal of 5 it is essentially planar. In the crystal structure of 4 the molecules related via an inversion centre form close dimers which pack in a severely distorted kappa-arrangement. Molecules of 5 assemble into uniform stacks with TTF moieties overlapping the side chains of adjacent molecules. Calculated geometries are in good agreement with the X-ray data, and the distortion from planarity in the crystal of 4 can be explained by nonbonding interactions between the amide substituent and the TTF rings of adjacent molecules. Evidence for intramolecular charge-transfer from the TTF ring to the electron-withdrawing amide and ester substituents of 4 and 5, respectively, is provided by UV-VIS spectroscopy in solution, analysis of the bond lengths in the crystal structure, and by theoretical calculations.",
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New functionalized tetrathiafulvalenes: X-ray crystal structures and physico-chemical properties of TTF-C(O)NMe2 and TTF-C(O)-O-C4H9: a joint experimental and theoretical study. / Batsanov, A.S.; Bryce, M.R.; Heaton, J.N.; Moore, A.J.; Skabara, P.J.; Howard, J.A.K.; Ortí, E.; Viruela, P.M.; Viruela, R.

In: Journal of Materials Chemistry, Vol. 5, No. 10, 1995, p. 1689-1696.

Research output: Contribution to journalArticle

TY - JOUR

T1 - New functionalized tetrathiafulvalenes: X-ray crystal structures and physico-chemical properties of TTF-C(O)NMe2 and TTF-C(O)-O-C4H9: a joint experimental and theoretical study

AU - Batsanov, A.S.

AU - Bryce, M.R.

AU - Heaton, J.N.

AU - Moore, A.J.

AU - Skabara, P.J.

AU - Howard, J.A.K.

AU - Ortí, E.

AU - Viruela, P.M.

AU - Viruela, R.

PY - 1995

Y1 - 1995

N2 - The synthesis of the new mono- and di-functionalized tetrathiafulvalene (TTF) derivatives 4, 5 and 12-15 is reported. Compounds 4 and 5 have been studied in detail: their single crystal X-ray structures are reported and theoretical calculations at both semiempirical and ab initio levels have been performed. The TTF moiety in the crystal of 4 is folded, whereas in the crystal of 5 it is essentially planar. In the crystal structure of 4 the molecules related via an inversion centre form close dimers which pack in a severely distorted kappa-arrangement. Molecules of 5 assemble into uniform stacks with TTF moieties overlapping the side chains of adjacent molecules. Calculated geometries are in good agreement with the X-ray data, and the distortion from planarity in the crystal of 4 can be explained by nonbonding interactions between the amide substituent and the TTF rings of adjacent molecules. Evidence for intramolecular charge-transfer from the TTF ring to the electron-withdrawing amide and ester substituents of 4 and 5, respectively, is provided by UV-VIS spectroscopy in solution, analysis of the bond lengths in the crystal structure, and by theoretical calculations.

AB - The synthesis of the new mono- and di-functionalized tetrathiafulvalene (TTF) derivatives 4, 5 and 12-15 is reported. Compounds 4 and 5 have been studied in detail: their single crystal X-ray structures are reported and theoretical calculations at both semiempirical and ab initio levels have been performed. The TTF moiety in the crystal of 4 is folded, whereas in the crystal of 5 it is essentially planar. In the crystal structure of 4 the molecules related via an inversion centre form close dimers which pack in a severely distorted kappa-arrangement. Molecules of 5 assemble into uniform stacks with TTF moieties overlapping the side chains of adjacent molecules. Calculated geometries are in good agreement with the X-ray data, and the distortion from planarity in the crystal of 4 can be explained by nonbonding interactions between the amide substituent and the TTF rings of adjacent molecules. Evidence for intramolecular charge-transfer from the TTF ring to the electron-withdrawing amide and ester substituents of 4 and 5, respectively, is provided by UV-VIS spectroscopy in solution, analysis of the bond lengths in the crystal structure, and by theoretical calculations.

KW - semiempirical methods

KW - kappa-phase

KW - parameters

KW - optimization

KW - derivatives

KW - molecules

KW - sulfur

KW - states

KW - MNDO

KW - TTF

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JF - Journal of Materials Chemistry

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