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Highly stable fullerene-based porous molecular crystals with open metal sites

DOI: 10.1038/s41563-019-0361-0 DOI Help

Authors: C. Grazia Bezzu (University of Edinburgh) , Luke A. Burt (University of Edinburgh) , Charles J. Mcmonagle (University of Edinburgh) , Stephen A. Moggach (University of Edinburgh) , Benson M. Kariuki (Cardiff University) , David R. Allan (Diamond Light Source) , Mark Warren (Diamond Light Source) , Neil B. Mckeown (University of Edinburgh)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nature Materials , VOL 348

State: Published (Approved)
Published: May 2019
Diamond Proposal Number(s): 9816 , 8945

Abstract: The synthesis of conventional porous crystals involves building a framework using reversible chemical bond formation, which can result in hydrolytic instability. In contrast, porous molecular crystals assemble using only weak intermolecular interactions, which generally do not provide the same environmental stability. Here, we report that the simple co-crystallization of a phthalocyanine derivative and a fullerene (C60 or C70) forms porous molecular crystals with environmental stability towards high temperature and hot aqueous base or acid. Moreover, by using diamond anvil cells and synchrotron single-crystal measurements, stability towards extreme pressure (>4 GPa) is demonstrated, with the stabilizing fullerene held between two phthalocyanines and the hold tightening at high pressure. Access to open metal centres within the porous molecular co-crystal is demonstrated by in situ crystallographic analysis of the chemisorption of pyridine, oxygen and carbon monoxide. This suggests strategies for the formation of highly stable and potentially functional porous materials using only weak van der Waals intermolecular interactions.

Journal Keywords: Carbon nanotubes and fullerenes; Coordination chemistry; Molecular self-assembly; Organic molecules in materials science; Porous materials

Subject Areas: Materials


Instruments: I19-Small Molecule Single Crystal Diffraction