Tetrathiafulvalenenaphthalenophanes: Planar chirality and cis/trans photoisomerization

R. Ballardini, V. Balzani, J. Becher, A. Di Fabio, M. T. Gandolfi, G. Mattersteig, M. B. Nielsen, F. M. Raymo, S. J. Rowan, J. F. Stoddart, A. J P White, D. J. Williams

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Abstract

A cyclophane incorporating one 1,5-dioxynaphthalene ring system and one tetrathiafulvalene (TTF) unit bridged by [SCH2CH2O] linkages has been synthesized. In this cyclophane, the TTF unit can adopt either cis or trans configurations. In addition, the 1,5-dioxynaphthalene ring system imposes one element of planar chirality on this cyclophane. A second element of planar chirality is introduced by the trans form of the TTF unit. Thus, the cyclophane exists in diastereoisomeric forms as three pairs of enantiomers. The enantiomeric pairs associated with the cis form of the TTF unit, as well as one of those associated with the trans form, have been isolated by crystallization, and their structures assigned in the solid state by single-crystal X-ray analyses. In solution, cis/trans isomerization occurs when either the cis or the trans form of the cyclophane is exposed to light. The photoisomerization reaction can be followed by 1H NMR and UV-vis spectroscopies, as well as by HPLC. The photoisomerization quantum yield has been measured at two different excitation wavelengths (406 and 313 nm). In both cases, the trans → cis process (φ = 0.20 at 406 nm) is much more efficient than the reverse cis → trans process (φ = 0.030 at 406 nm). Since the absorption spectra of the trans and cis isomers are different and the quantum yield of the trans → cis photoisomerization reaction depends on the excitation wavelength, the mole fraction of the two diastereoisomers present at the photostationary state depends on the wavelength of the exciting light. No isomerization occurs when the solutions, regardless of the mole fraction of the two diastereoisomers, are stored in the dark.

Original languageEnglish
Pages (from-to)4120-4126
Number of pages7
JournalJournal of Organic Chemistry
Volume65
Issue number13
DOIs
Publication statusPublished - 2000 Jun 30
Externally publishedYes

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ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Ballardini, R., Balzani, V., Becher, J., Di Fabio, A., Gandolfi, M. T., Mattersteig, G., Nielsen, M. B., Raymo, F. M., Rowan, S. J., Stoddart, J. F., White, A. J. P., & Williams, D. J. (2000). Tetrathiafulvalenenaphthalenophanes: Planar chirality and cis/trans photoisomerization. Journal of Organic Chemistry, 65(13), 4120-4126. https://doi.org/10.1021/jo0001941