Ion-regulated allosteric binding of fullerenes (C60 and C 70) by tetrathiafulvalene-calix[4]pyrroles

Christina M. Davis, Jong Min Lim, Karina R. Larsen, Dong Sub Kim, Young Mo Sung, Dani M. Lyons, Vincent M. Lynch, Kent A. Nielsen, Jan O. Jeppesen, Dongho Kim, Jung Su Park, Jonathan L. Sessler

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

The effect of ionic species on the binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single crystal X-ray diffraction methods and in dichloromethane solution by means of continuous variation plots and UV-vis spectroscopic titrations. These analyses revealed a 1:1 stoichiometry between the anion-bound TTF-C4Ps and the complexed fullerenes. The latter guests are bound within the bowl-like cup of the C4P in a ball-and-socket binding mode. The interactions between the TTF-C4P receptors and the fullerene guests are highly influenced by both the nature of halide anions and their counter tetraalkylammonium cations. Three halides (F-, Cl-, and Br-) were studied. All three potentiate the binding of the two test fullerenes by inducing a conformational change from the 1,3-alternate to the cone conformer of the TTF-C4Ps, thus acting as positive heterotropic allosteric effectors. For a particular halide anion, the choice of tetraalkylammonium salts serves to modulate the strength of the TTF-C4P-fullerene host-guest binding interactions and, in conjunction with variations in the halide anion, can be exploited to alter the inherent selectivity of the host for a given fullerene. Differences in binding are reflected in the excited state optical properties. Overall, the present four-component system provides an illustration of how host-guest binding events involving appropriately designed artificial receptors can be fine-tuned via the addition of simple ionic species as allosteric modulators.

Original languageEnglish
Pages (from-to)10410-10417
Number of pages8
JournalJournal of the American Chemical Society
Volume136
Issue number29
DOIs
Publication statusPublished - 2014 Jul 23

Fingerprint

Fullerenes
Anions
Ions
Negative ions
Cations
Artificial Receptors
Positive ions
Methylene Chloride
Titration
Excited states
X-Ray Diffraction
Stoichiometry
Dichloromethane
Modulators
fullerene C60
tetrathiafulvalene calix(4)pyrrole
Cones
Optical properties
Salts
Single crystals

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Davis, C. M., Lim, J. M., Larsen, K. R., Kim, D. S., Sung, Y. M., Lyons, D. M., ... Sessler, J. L. (2014). Ion-regulated allosteric binding of fullerenes (C60 and C 70) by tetrathiafulvalene-calix[4]pyrroles. Journal of the American Chemical Society, 136(29), 10410-10417. https://doi.org/10.1021/ja504077f
Davis, Christina M. ; Lim, Jong Min ; Larsen, Karina R. ; Kim, Dong Sub ; Sung, Young Mo ; Lyons, Dani M. ; Lynch, Vincent M. ; Nielsen, Kent A. ; Jeppesen, Jan O. ; Kim, Dongho ; Park, Jung Su ; Sessler, Jonathan L. / Ion-regulated allosteric binding of fullerenes (C60 and C 70) by tetrathiafulvalene-calix[4]pyrroles. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 29. pp. 10410-10417.
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abstract = "The effect of ionic species on the binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single crystal X-ray diffraction methods and in dichloromethane solution by means of continuous variation plots and UV-vis spectroscopic titrations. These analyses revealed a 1:1 stoichiometry between the anion-bound TTF-C4Ps and the complexed fullerenes. The latter guests are bound within the bowl-like cup of the C4P in a ball-and-socket binding mode. The interactions between the TTF-C4P receptors and the fullerene guests are highly influenced by both the nature of halide anions and their counter tetraalkylammonium cations. Three halides (F-, Cl-, and Br-) were studied. All three potentiate the binding of the two test fullerenes by inducing a conformational change from the 1,3-alternate to the cone conformer of the TTF-C4Ps, thus acting as positive heterotropic allosteric effectors. For a particular halide anion, the choice of tetraalkylammonium salts serves to modulate the strength of the TTF-C4P-fullerene host-guest binding interactions and, in conjunction with variations in the halide anion, can be exploited to alter the inherent selectivity of the host for a given fullerene. Differences in binding are reflected in the excited state optical properties. Overall, the present four-component system provides an illustration of how host-guest binding events involving appropriately designed artificial receptors can be fine-tuned via the addition of simple ionic species as allosteric modulators.",
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Davis, CM, Lim, JM, Larsen, KR, Kim, DS, Sung, YM, Lyons, DM, Lynch, VM, Nielsen, KA, Jeppesen, JO, Kim, D, Park, JS & Sessler, JL 2014, 'Ion-regulated allosteric binding of fullerenes (C60 and C 70) by tetrathiafulvalene-calix[4]pyrroles', Journal of the American Chemical Society, vol. 136, no. 29, pp. 10410-10417. https://doi.org/10.1021/ja504077f

Ion-regulated allosteric binding of fullerenes (C60 and C 70) by tetrathiafulvalene-calix[4]pyrroles. / Davis, Christina M.; Lim, Jong Min; Larsen, Karina R.; Kim, Dong Sub; Sung, Young Mo; Lyons, Dani M.; Lynch, Vincent M.; Nielsen, Kent A.; Jeppesen, Jan O.; Kim, Dongho; Park, Jung Su; Sessler, Jonathan L.

In: Journal of the American Chemical Society, Vol. 136, No. 29, 23.07.2014, p. 10410-10417.

Research output: Contribution to journalArticle

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AU - Davis, Christina M.

AU - Lim, Jong Min

AU - Larsen, Karina R.

AU - Kim, Dong Sub

AU - Sung, Young Mo

AU - Lyons, Dani M.

AU - Lynch, Vincent M.

AU - Nielsen, Kent A.

AU - Jeppesen, Jan O.

AU - Kim, Dongho

AU - Park, Jung Su

AU - Sessler, Jonathan L.

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