Stable Encapsulation of Acrylate Esters in Networked Molecular Capsules

Abstract

Reactive acrylate esters were encapsulated in the cavity of networked molecular capsules in a single-crystal-to-single-crystal fashion. Owing to the encapsulation effect, acrylates inside the capsules do not undergo polymerization upon irradiation with UV light or heating, while the guest molecules can be quantitatively extracted by treatment with toluene.

Tunable Keplerate Type‐Cluster “Mo132” Cavity with Dicarboxylate Anions

“…In this field, Fujita and Raymond reported on many discrete nano‐sized hybrid compounds directed by the basic principles of supramolecular coordination chemistry. Such an approach gave rise to a wide set of topologies including squares, tetrahedral, rings and spheres 1–6. In addition to their highly symmetric and aesthetic shape, these nanometric hollow clusters behave as functional nanoflask for catalysis and specific chemical transformations.…”

Emerging applications of metal–organic frameworks

“…However, the potential to inspect unstable moieties or molecules that are not easily crystallised in pure form is highly attractive, and a range of targets has been recently investigated to further demonstrate the utility of the strategy. [54][55][56][57][58][59][60][61] The characterised guest molecules range from simple molecules 54 to reactive acrylate esters 56 and complex Please do not adjust margins Please do not adjust margins molecules with axial and planar chirality, 58 (1R)-(-)-menthyl acetate, 59 α-humulene and its oxidized subproducts. 60 The 'crystalline sponge' approach has also been developed for porous organic materials 61 mirroring studies in MOFs.…”

X‐ray Crystallography in Open‐Framework Materials

“…Despite these reservations the unique environment provided by framework pores offers abroad scope for using the "crystal-sponge" strategy to analyze unstable moieties that otherwise would not be amenable to X-ray analysis.A n example of this stabilizing effect has been reported by Ning et al [18] who infiltrated and structurally characterized reactive acrylate esters within af ramework material. In addition to post-synthetically encapsulating molecules within pore voids the molecular architecture of frameworks can be utilized to lock functionalized molecular cartridges between their walls.…”

“…Theu se of ac artridge approach by Fujita et al [12,18] demonstrates the importance of such framework-guest interactions.T hus,t oe xpand the application of this methodology,n ew frameworks will need to be synthesized that encompass ab roader range of pore volumes and surface chemistries.H owever,g iven the expansive library of known framework materials [26] and ad eep understanding of host-guest chemistry garnered from discrete systems,itcan be anticipated that bespoke "crystalline sponges" can be synthesized that target guests of varied size and chemistry.W enote that poor data quality can preclude precise assignment of molecular connectivity or stereochemistry of guests (particularly flexible molecules) in porous frameworks. Theu se of ac artridge approach by Fujita et al [12,18] demonstrates the importance of such framework-guest interactions.T hus,t oe xpand the application of this methodology,n ew frameworks will need to be synthesized that encompass ab roader range of pore volumes and surface chemistries.H owever,g iven the expansive library of known framework materials [26] and ad eep understanding of host-guest chemistry garnered from discrete systems,itcan be anticipated that bespoke "crystalline sponges" can be synthesized that target guests of varied size and chemistry.W enote that poor data quality can preclude precise assignment of molecular connectivity or stereochemistry of guests (particularly flexible molecules) in porous frameworks.…”