Improving the gas sorption capacity in lantern-type metal-organic polyhedra by a scrambled cage method.

16 November 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The synthesis of multivariate metal-organic frameworks (MOFs) is a well-known method for increasing the complexity of porous frameworks. In these materials, the structural differences of the ligands used in the synthesis are sufficiently subtle that they can each occupy the same site in the framework. However, multivariate or ligand scrambling approaches are rarely used in the synthesis of porous metal-organic polyhedra (MOPs) – the molecular equivalent of MOFs – despite the potential to retain a unique intrinsic pore from the individual cage while varying the extrinsic porosity of the material. Herein we directly synthesise scrambled cages across two families of lantern-type MOPs and find contrasting effects on their gas sorption properties. In one family, the scrambling approach sees a gradual increase in the BET surface area with the maximum and minimum uptakes associated with the two pure homoleptic cages. In the other, the scrambled materials display improved surface areas with respect to both of the original, homoleptic cages. Through analysis of the gas sorption isotherms, we attribute this effect to the balance of micro- and mesoporosity with the materials. The gas uptake of the materials presented here underscores the tunability of cages that springs from their combination of intrinsic, extrinsic, micro- and meso- porosities.


Porous materials
metal-organic polyhedra
metal-organic cages
supramolecular chemistry

Supplementary materials

Supporting information for “Improving the gas sorption capacity in lantern-type metal-organic polyhedra by a scrambled cage method.”
Additional IR spectra, PXRD data, 1H-NMR spectra, TGA data, details of crystallographic structure resolution, additional gas sorption measurements, and analysis of surface areas.


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