Triangular Regulation of Cucurbit[8]uril 1:1 Complexes

Sébastien Combes, Khoa Truong Tran, Mehmet Menaf Ayhan, Hakim Karoui, A. Rockenbauer, Alain Tonetto, Valérie Monnier, Laurence Charles, Roselyne Rosas, Stéphane Viel, Didier Siri, Paul Tordo, Sylvain Clair, Ruibing Wang, David Bardelang, Olivier Ouari

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Triangular shapes have inspired scientists over time and are common in nature, such as the flower petals of oxalis triangularis, the triangular faces of tetrahedrite crystals, and the icosahedron faces of virus capsids. Supramolecular chemistry has enabled the construction of triangular assemblies, many of which possess functional features. Among these structures, cucurbiturils have been used to build supramolecular triangles, and we recently reported paramagnetic cucurbit[8]uril (CB[8]) triangles, but the reasons for their formation remain unclear. Several parameters have now been identified to explain their formation. At first sight, the radical nature of the guest was of prime importance in obtaining the triangles, and we focused on extending this concept to biradicals to get supramolecular hexaradicals. Two sodium ions were systematically observed by ESI-MS in trimer structures, and the presence of Na + triggered or strengthened the triangulation of CB[8]/guest 1:1 complexes in solution. X-ray crystallography and molecular modeling have allowed the proposal of two plausible sites of residence for the two sodium cations. We then found that a diamagnetic guest with an H-bond acceptor function is equally good at forming CB[8] triangles. Hence, a guest molecule containing a ketone function has been precisely triangulated thanks to CB[8] and sodium cations as determined by DOSY-NMR and DLS. A binding constant for the triangulation of 1:1 to 3:3 complexes is proposed. This concept has finally been extended to the triangulation of ditopic guests toward network formation by the reticulation of CB[8] triangles using dinitroxide biradicals.

Original languageEnglish
JournalJournal of the American Chemical Society
DOIs
Publication statusPublished - Jan 1 2019

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Triangulation
Sodium
Supramolecular chemistry
Positive ions
Molecular modeling
X ray crystallography
Cations
Ketones
Viruses
Nuclear magnetic resonance
Capsid
X Ray Crystallography
Crystals
Molecules
Ions
cucurbit(8)uril

ASJC Scopus subject areas

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

Cite this

Triangular Regulation of Cucurbit[8]uril 1:1 Complexes. / Combes, Sébastien; Tran, Khoa Truong; Ayhan, Mehmet Menaf; Karoui, Hakim; Rockenbauer, A.; Tonetto, Alain; Monnier, Valérie; Charles, Laurence; Rosas, Roselyne; Viel, Stéphane; Siri, Didier; Tordo, Paul; Clair, Sylvain; Wang, Ruibing; Bardelang, David; Ouari, Olivier.

In: Journal of the American Chemical Society, 01.01.2019.

Research output: Contribution to journalArticle

Combes, S, Tran, KT, Ayhan, MM, Karoui, H, Rockenbauer, A, Tonetto, A, Monnier, V, Charles, L, Rosas, R, Viel, S, Siri, D, Tordo, P, Clair, S, Wang, R, Bardelang, D & Ouari, O 2019, 'Triangular Regulation of Cucurbit[8]uril 1:1 Complexes', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b00150
Combes, Sébastien ; Tran, Khoa Truong ; Ayhan, Mehmet Menaf ; Karoui, Hakim ; Rockenbauer, A. ; Tonetto, Alain ; Monnier, Valérie ; Charles, Laurence ; Rosas, Roselyne ; Viel, Stéphane ; Siri, Didier ; Tordo, Paul ; Clair, Sylvain ; Wang, Ruibing ; Bardelang, David ; Ouari, Olivier. / Triangular Regulation of Cucurbit[8]uril 1:1 Complexes. In: Journal of the American Chemical Society. 2019.
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AU - Siri, Didier

AU - Tordo, Paul

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AU - Ouari, Olivier

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