Complexation of polyoxometalates with cyclodextrins

Wu, Yilei ORCID: https://orcid.org/0000-0003-0253-1625, Shi, Rufei, Wu, Yi-Lin ORCID: https://orcid.org/0000-0003-0253-1625, Holcroft, James M., Liu, Zhichang, Frasconi, Marco, Wasielewski, Michael R., Li, Hui and Stoddart, J. Fraser 2015. Complexation of polyoxometalates with cyclodextrins. Journal of the American Chemical Society 137 (12) , pp. 4111-4118. 10.1021/ja511713c

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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]⊂[γ-CD]2} (CD-POM-1) and [La(H2O)9] {[PMo12O40]⊂[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═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. 1 Introduction

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0002-7863
Last Modified:	13 Jan 2023 02:32
URI:	https://orca.cardiff.ac.uk/id/eprint/118251

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