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Article Dans Une Revue Journal of the American Chemical Society Année : 2022

Chaotropic Effect as Assembly Motif to Construct Supramolecular Cyclodextrin-Polyoxometalate based Frameworks

Mohamed Haouas
William Shepard
Clement Falaise
Emmanuel Cadot

Résumé

In aqueous solution, low charged polyoxometalates (POMs) exhibit remarkable self-assembly properties with non-ionic organic matter that have been recently used to develop groundbreaking advances in host-guest chemistry, as well as in soft matter science. Herein, we exploit the affinity between chaotropic POM and native cyclodextrins (α-, β-, and γ-CD) to enhance the structural and functional diversity of cyclodextrin-based open frameworks. At first, we reveal that the Anderson-Evans type polyoxometalate [AlMo6O18(OH)6] 3represents an efficient inorganic scaffold to design open hybrid frameworks built from infinite cyclodextrin channels connected through the disc-shaped POM. Single-crystal X-ray analysis demonstrates that the resulting supramolecular architectures contain large cavities (up to 2 nm) where the topologies are dictated by the rotational symmetry of the organic macrocycle, generating honeycomb-(bnn net) or checkerboards-like (pcu net) networks for α-CD (C6) or γ-CD (C8), respectively. On the other hand, the use of β-CD, a macrocycle with C7 ideal symmetry, led to a distorted checkerboard-like network. The cyclodextrin-based frameworks built from Anderson-Evans type POM are easily functionalizable using the molecular recognition properties of the macrocycle building units. As proof of concept, we successfully isolated a series of compartmentalized functional frameworks by the entrapment of poly-iodides or superchaotropic redox-active polyanions within the macrocyclic hosting matrix. This set of results paves the way for designing multifunctional supramolecular frameworks whose pore dimensions are controlled by the size of inorganic entities.

Domaines

Matériaux
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Dates et versions

hal-03645356 , version 1 (19-04-2022)

Identifiants

Citer

Soumaya Khlifi, Jérôme Marrot, Mohamed Haouas, William Shepard, Clement Falaise, et al.. Chaotropic Effect as Assembly Motif to Construct Supramolecular Cyclodextrin-Polyoxometalate based Frameworks. Journal of the American Chemical Society, 2022, 144 (10), pp.4469-4477. ⟨10.1021/jacs.1c12049⟩. ⟨hal-03645356⟩
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