Switchable gate-opening effect in metal–organic polyhedra assemblies through solution processing

Craig, Gavin A. and Larpent, Patrick and Kusaka, Shinpei and Matsuda, Ryotaro and Kitagawa, Susumu and Furukawa, Shuhei (2018) Switchable gate-opening effect in metal–organic polyhedra assemblies through solution processing. Chemical Science, 9 (31). pp. 6463-6469. ISSN 2041-6520 (https://doi.org/10.1039/C8SC02263A)

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Gate-opening gas sorption is known for metal–organic frameworks, and is associated with structural flexibility and advantageous properties for sensing and gas uptake. Here, we show that gate-opening is also possible for metal–organic polyhedra (MOPs), and depends on the molecular organisation in the lattice. Thanks to the solubility of MOPs, several interchangeable solvatomorphs of a lantern-type MOP were synthesised via treatment with different solvents. One phase obtained through use of methanol induced a gate-opening effect in the lattice in response to carbon dioxide uptake. The sorption process was thoroughly investigated with in situ powder X-ray diffraction and simultaneous adsorption experiments. Meanwhile, solution processing of this flexible phase using THF led to a permanently porous phase without a gate-opening effect. Furthermore, we find that we can change the metallic composition of the MOP, and yet retain flexibility. By showing that gate-opening can be switched on and off depending on the solvent of crystallisation, these findings have implications for the solution-based processing of MOPs.