Donor-substituted cyanoethynylethenes: π-conjugation and band-gap tuning in strong charge-transfer chromophores

Nicolle N.P. Moonen, William C. Pomerantz, Robin Gist, Corinne Boudon, Jean Paul Gisselbrecht, Tsuyoshi Kawai, Atsushi Kishioka, Maurice Gross, Masahiro Irie, François Diederich

Research output: Contribution to journalArticle

88 Citations (Scopus)

Abstract

An extensive series of silyl-protected cyanoethynylethenes (CEEs) and N,N-dimethylanilino donor-substituted CEEs have been synthesized. More extended chromophores were constructed by selective silyl deprotection and subsequent oxidative acetylenic coupling. The strong electron-accepting nature of the CEEs was revealed by a combination of 13C NMR spectro-scopic and electrochemistry measurements. Donor-substituted CEEs display strong intramolecular charge-transfer (CT) character, resulting in intense, bathochromically shifted CT bands in the UV/Vis spectrum. Their structural diversity establishes them as suitable models for the study of π-conjugation and band gap tuning in strong charge-transfer chromophores. The extent of π-conjugation in the donor-substituted CEEs was investigated by a combination of ground-state techniques, such as X-ray crystallography, electrochemistry, B3 LYP calculations, and NMR spectroscopy. The comparison of these ground-state results with the features observed in the UV/Vis spectra reveals that - contrary to expectations - more extensive π - conjugation can lead to larger band gaps in molecules with strong donor and acceptor moieties.

Original languageEnglish (US)
Pages (from-to)3325-3341
Number of pages17
JournalChemistry - A European Journal
Volume11
Issue number11
DOIs
StatePublished - May 20 2005

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Chromophores
Charge transfer
Energy gap
Tuning
Electrochemistry
Ground state
X ray crystallography
Nuclear magnetic resonance spectroscopy
Nuclear magnetic resonance
Molecules
Electrons

Keywords

  • Alkynes
  • Charge transfer
  • Conjugation
  • Electrochemistry
  • Two-photon absorption

Cite this

Donor-substituted cyanoethynylethenes : π-conjugation and band-gap tuning in strong charge-transfer chromophores. / Moonen, Nicolle N.P.; Pomerantz, William C.; Gist, Robin; Boudon, Corinne; Gisselbrecht, Jean Paul; Kawai, Tsuyoshi; Kishioka, Atsushi; Gross, Maurice; Irie, Masahiro; Diederich, François.

In: Chemistry - A European Journal, Vol. 11, No. 11, 20.05.2005, p. 3325-3341.

Research output: Contribution to journalArticle

Moonen, NNP, Pomerantz, WC, Gist, R, Boudon, C, Gisselbrecht, JP, Kawai, T, Kishioka, A, Gross, M, Irie, M & Diederich, F 2005, 'Donor-substituted cyanoethynylethenes: π-conjugation and band-gap tuning in strong charge-transfer chromophores', Chemistry - A European Journal, vol. 11, no. 11, pp. 3325-3341. https://doi.org/10.1002/chem.200500082
Moonen, Nicolle N.P. ; Pomerantz, William C. ; Gist, Robin ; Boudon, Corinne ; Gisselbrecht, Jean Paul ; Kawai, Tsuyoshi ; Kishioka, Atsushi ; Gross, Maurice ; Irie, Masahiro ; Diederich, François. / Donor-substituted cyanoethynylethenes : π-conjugation and band-gap tuning in strong charge-transfer chromophores. In: Chemistry - A European Journal. 2005 ; Vol. 11, No. 11. pp. 3325-3341.
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