Studies on the dynamics of phosphorylated p-tert-butylcalix[6]arenes by using 2D NMR spectroscopy

R.G. Janssen, Rob G. Janssen, John P.M. van Duynhoven, J.P.M. van Duynhoven, Willem Verboom, G.J. van Hummel, Sybolt Harkema, David Reinhoudt

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Abstract

The overall dynamics of partially phosphorylated and thiophosphorylated p-tert-butylcalix[6]arenes has been studied by NMR spectroscopy. When p-tert-butylcalix[6]arene is monosubstituted with a phosphate or thiophosphate group, the calix[6]arene skeleton is remarkably rigidified. The 1,3- and 1,4-(thio)phosphorylated p-tert-butylcalix[6]arenes are more flexible. 2D NMR spectroscopy showed that these calix[6]arenes adopt syn conformations. A combination of 1H and 31P NMR spectroscopy revealed that the calix[6]arene (thio)phosphates are involved in at least three dynamic processes, viz., macrocyclic ring interconversion, hydrogen bond array reversal, and pinched conformer interconversion. The activation barrier (ΔGm) for macrocyclic ring interconversion depends on the type and number of substituents and ranges from 67 to 86 kJ·mol-1. The activation barrier (ΔGh) for hydrogen bond array reversal depends on the number of hydroxyl groups and ranges from 31 to 45 kJ·mol-1. For the pinched conformer interconversion an activation barrier (ΔGp) ranging from 44 to 55 kJ·mol-1 was found. Pinched conformations have been frequently observed in the solid state, for example, for mono- and 1,4-bis(thiophosphorylated) p-tert-butylcalix[6]arene. These studies, however, show for the first time that these conformations also exist in solution and that differently pinched conformers may rapidly interconvert.
Original languageUndefined
Pages (from-to)3666-3675
JournalJournal of the American Chemical Society
Volume118
Issue number118
DOIs
Publication statusPublished - 1996

Keywords

  • METIS-105891
  • IR-10894

Cite this

Janssen, R.G. ; Janssen, Rob G. ; van Duynhoven, John P.M. ; van Duynhoven, J.P.M. ; Verboom, Willem ; van Hummel, G.J. ; Harkema, Sybolt ; Reinhoudt, David. / Studies on the dynamics of phosphorylated p-tert-butylcalix[6]arenes by using 2D NMR spectroscopy. In: Journal of the American Chemical Society. 1996 ; Vol. 118, No. 118. pp. 3666-3675.
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title = "Studies on the dynamics of phosphorylated p-tert-butylcalix[6]arenes by using 2D NMR spectroscopy",
abstract = "The overall dynamics of partially phosphorylated and thiophosphorylated p-tert-butylcalix[6]arenes has been studied by NMR spectroscopy. When p-tert-butylcalix[6]arene is monosubstituted with a phosphate or thiophosphate group, the calix[6]arene skeleton is remarkably rigidified. The 1,3- and 1,4-(thio)phosphorylated p-tert-butylcalix[6]arenes are more flexible. 2D NMR spectroscopy showed that these calix[6]arenes adopt syn conformations. A combination of 1H and 31P NMR spectroscopy revealed that the calix[6]arene (thio)phosphates are involved in at least three dynamic processes, viz., macrocyclic ring interconversion, hydrogen bond array reversal, and pinched conformer interconversion. The activation barrier (ΔGm) for macrocyclic ring interconversion depends on the type and number of substituents and ranges from 67 to 86 kJ·mol-1. The activation barrier (ΔGh) for hydrogen bond array reversal depends on the number of hydroxyl groups and ranges from 31 to 45 kJ·mol-1. For the pinched conformer interconversion an activation barrier (ΔGp) ranging from 44 to 55 kJ·mol-1 was found. Pinched conformations have been frequently observed in the solid state, for example, for mono- and 1,4-bis(thiophosphorylated) p-tert-butylcalix[6]arene. These studies, however, show for the first time that these conformations also exist in solution and that differently pinched conformers may rapidly interconvert.",
keywords = "METIS-105891, IR-10894",
author = "R.G. Janssen and Janssen, {Rob G.} and {van Duynhoven}, {John P.M.} and {van Duynhoven}, J.P.M. and Willem Verboom and {van Hummel}, G.J. and Sybolt Harkema and David Reinhoudt",
year = "1996",
doi = "10.1021/ja9540942",
language = "Undefined",
volume = "118",
pages = "3666--3675",
journal = "Journal of the American Chemical Society",
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Janssen, RG, Janssen, RG, van Duynhoven, JPM, van Duynhoven, JPM, Verboom, W, van Hummel, GJ, Harkema, S & Reinhoudt, D 1996, 'Studies on the dynamics of phosphorylated p-tert-butylcalix[6]arenes by using 2D NMR spectroscopy', Journal of the American Chemical Society, vol. 118, no. 118, pp. 3666-3675. https://doi.org/10.1021/ja9540942

Studies on the dynamics of phosphorylated p-tert-butylcalix[6]arenes by using 2D NMR spectroscopy. / Janssen, R.G.; Janssen, Rob G.; van Duynhoven, John P.M.; van Duynhoven, J.P.M.; Verboom, Willem; van Hummel, G.J.; Harkema, Sybolt; Reinhoudt, David.

In: Journal of the American Chemical Society, Vol. 118, No. 118, 1996, p. 3666-3675.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Studies on the dynamics of phosphorylated p-tert-butylcalix[6]arenes by using 2D NMR spectroscopy

AU - Janssen, R.G.

AU - Janssen, Rob G.

AU - van Duynhoven, John P.M.

AU - van Duynhoven, J.P.M.

AU - Verboom, Willem

AU - van Hummel, G.J.

AU - Harkema, Sybolt

AU - Reinhoudt, David

PY - 1996

Y1 - 1996

N2 - The overall dynamics of partially phosphorylated and thiophosphorylated p-tert-butylcalix[6]arenes has been studied by NMR spectroscopy. When p-tert-butylcalix[6]arene is monosubstituted with a phosphate or thiophosphate group, the calix[6]arene skeleton is remarkably rigidified. The 1,3- and 1,4-(thio)phosphorylated p-tert-butylcalix[6]arenes are more flexible. 2D NMR spectroscopy showed that these calix[6]arenes adopt syn conformations. A combination of 1H and 31P NMR spectroscopy revealed that the calix[6]arene (thio)phosphates are involved in at least three dynamic processes, viz., macrocyclic ring interconversion, hydrogen bond array reversal, and pinched conformer interconversion. The activation barrier (ΔGm) for macrocyclic ring interconversion depends on the type and number of substituents and ranges from 67 to 86 kJ·mol-1. The activation barrier (ΔGh) for hydrogen bond array reversal depends on the number of hydroxyl groups and ranges from 31 to 45 kJ·mol-1. For the pinched conformer interconversion an activation barrier (ΔGp) ranging from 44 to 55 kJ·mol-1 was found. Pinched conformations have been frequently observed in the solid state, for example, for mono- and 1,4-bis(thiophosphorylated) p-tert-butylcalix[6]arene. These studies, however, show for the first time that these conformations also exist in solution and that differently pinched conformers may rapidly interconvert.

AB - The overall dynamics of partially phosphorylated and thiophosphorylated p-tert-butylcalix[6]arenes has been studied by NMR spectroscopy. When p-tert-butylcalix[6]arene is monosubstituted with a phosphate or thiophosphate group, the calix[6]arene skeleton is remarkably rigidified. The 1,3- and 1,4-(thio)phosphorylated p-tert-butylcalix[6]arenes are more flexible. 2D NMR spectroscopy showed that these calix[6]arenes adopt syn conformations. A combination of 1H and 31P NMR spectroscopy revealed that the calix[6]arene (thio)phosphates are involved in at least three dynamic processes, viz., macrocyclic ring interconversion, hydrogen bond array reversal, and pinched conformer interconversion. The activation barrier (ΔGm) for macrocyclic ring interconversion depends on the type and number of substituents and ranges from 67 to 86 kJ·mol-1. The activation barrier (ΔGh) for hydrogen bond array reversal depends on the number of hydroxyl groups and ranges from 31 to 45 kJ·mol-1. For the pinched conformer interconversion an activation barrier (ΔGp) ranging from 44 to 55 kJ·mol-1 was found. Pinched conformations have been frequently observed in the solid state, for example, for mono- and 1,4-bis(thiophosphorylated) p-tert-butylcalix[6]arene. These studies, however, show for the first time that these conformations also exist in solution and that differently pinched conformers may rapidly interconvert.

KW - METIS-105891

KW - IR-10894

U2 - 10.1021/ja9540942

DO - 10.1021/ja9540942

M3 - Article

VL - 118

SP - 3666

EP - 3675

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 118

ER -