Complexation of polyoxometalates with cyclodextrins

Yilei Wu, Rufei Shi, Yi Lin Wu, James M. Holcroft, Zhichang Liu, Marco Frasconi, Michael R Wasielewski, Hui Li, J. Fraser Stoddart

Research output: Contribution to journalArticle

64 Citations (Scopus)

Abstract

Although complexation of hydrophilic guests inside the cavities of hydrophobic hosts is considered to be unlikely, we demonstrate herein the complexation between γ- and β-cyclodextrins (γ- and β-CDs) with an archetypal polyoxometalate (POM) - namely, the [PMo12O40]3- trianion - which has led to the formation of two organic-inorganic hybrid 2:1 complexes, namely [La(H2O)9]{[PMo12O40]âŠ⊂[γ-CD]2} (CD-POM-1) and [La(H2O)9] {[PMo12O40]âŠ⊂[β-CD]2} (CD-POM-2), in the solid state. The extent to which these complexes assemble in solution has been investigated by (i) 1H, 13C, and 31P NMR spectroscopies and (ii) small- and wide-angle X-ray scattering, as well as (iii) mass spectrometry. Single-crystal X-ray diffraction reveals that both complexes have a sandwich-like structure, wherein one [PMo12O40]3- trianion is encapsulated by the primary faces of two CD tori through intermolecular [C-H···Oî - Mo] interactions. X-ray crystal superstructures of CD-POM-1 and CD-POM-2 show also that both of these 2:1 complexes are lined up longitudinally in a one-dimensional columnar fashion by means of [O-H···O] interactions. A beneficial nanoconfinement-induced stabilizing effect is supported by the observation of slow color changes for these supermolecules in aqueous solution phase. Electrochemical studies show that the redox properties of [PMo12O40]3- trianions encapsulated by CDs in the complexes are largely preserved in solution. The supramolecular complementarity between the CDs and the [PMo12O40]3- trianion provides yet another opportunity for the functionalization of POMs under mild conditions by using host-guest chemistry.

Original languageEnglish
Pages (from-to)4111-4118
Number of pages8
JournalJournal of the American Chemical Society
Volume137
Issue number12
DOIs
Publication statusPublished - Apr 1 2015

Fingerprint

Cyclodextrins
Complexation
X ray scattering
Nuclear magnetic resonance spectroscopy
Mass spectrometry
X-Rays
Single crystals
Color
X ray diffraction
X rays
Crystals
X-Ray Diffraction
Oxidation-Reduction
Mass Spectrometry
Magnetic Resonance Spectroscopy
Observation
polyoxometalate I
(PMo12O40)3-

ASJC Scopus subject areas

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

Cite this

Wu, Y., Shi, R., Wu, Y. L., Holcroft, J. M., Liu, Z., Frasconi, M., ... Stoddart, J. F. (2015). Complexation of polyoxometalates with cyclodextrins. Journal of the American Chemical Society, 137(12), 4111-4118. https://doi.org/10.1021/ja511713c

Complexation of polyoxometalates with cyclodextrins. / Wu, Yilei; Shi, Rufei; Wu, Yi Lin; Holcroft, James M.; Liu, Zhichang; Frasconi, Marco; Wasielewski, Michael R; Li, Hui; Stoddart, J. Fraser.

In: Journal of the American Chemical Society, Vol. 137, No. 12, 01.04.2015, p. 4111-4118.

Research output: Contribution to journalArticle

Wu, Y, Shi, R, Wu, YL, Holcroft, JM, Liu, Z, Frasconi, M, Wasielewski, MR, Li, H & Stoddart, JF 2015, 'Complexation of polyoxometalates with cyclodextrins', Journal of the American Chemical Society, vol. 137, no. 12, pp. 4111-4118. https://doi.org/10.1021/ja511713c
Wu Y, Shi R, Wu YL, Holcroft JM, Liu Z, Frasconi M et al. Complexation of polyoxometalates with cyclodextrins. Journal of the American Chemical Society. 2015 Apr 1;137(12):4111-4118. https://doi.org/10.1021/ja511713c
Wu, Yilei ; Shi, Rufei ; Wu, Yi Lin ; Holcroft, James M. ; Liu, Zhichang ; Frasconi, Marco ; Wasielewski, Michael R ; Li, Hui ; Stoddart, J. Fraser. / Complexation of polyoxometalates with cyclodextrins. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 12. pp. 4111-4118.
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abstract = "Although complexation of hydrophilic guests inside the cavities of hydrophobic hosts is considered to be unlikely, we demonstrate herein the complexation between γ- and β-cyclodextrins (γ- and β-CDs) with an archetypal polyoxometalate (POM) - namely, the [PMo12O40]3- trianion - which has led to the formation of two organic-inorganic hybrid 2:1 complexes, namely [La(H2O)9]{[PMo12O40]{\^a}Š⊂[γ-CD]2} (CD-POM-1) and [La(H2O)9] {[PMo12O40]{\^a}Š⊂[β-CD]2} (CD-POM-2), in the solid state. The extent to which these complexes assemble in solution has been investigated by (i) 1H, 13C, and 31P NMR spectroscopies and (ii) small- and wide-angle X-ray scattering, as well as (iii) mass spectrometry. Single-crystal X-ray diffraction reveals that both complexes have a sandwich-like structure, wherein one [PMo12O40]3- trianion is encapsulated by the primary faces of two CD tori through intermolecular [C-H···O{\^i} - Mo] interactions. X-ray crystal superstructures of CD-POM-1 and CD-POM-2 show also that both of these 2:1 complexes are lined up longitudinally in a one-dimensional columnar fashion by means of [O-H···O] interactions. A beneficial nanoconfinement-induced stabilizing effect is supported by the observation of slow color changes for these supermolecules in aqueous solution phase. Electrochemical studies show that the redox properties of [PMo12O40]3- trianions encapsulated by CDs in the complexes are largely preserved in solution. The supramolecular complementarity between the CDs and the [PMo12O40]3- trianion provides yet another opportunity for the functionalization of POMs under mild conditions by using host-guest chemistry.",
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