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.
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Crystallographic data are available free of charge from the Cambridge Crystallographic Data Centre (CCDC) http://www.ccdc.cam.ac.uk/data_request/cif by using the following deposition codes. CCDC1851707: non cubic form of (dipPhO)8PcH2 (Supplementary Table 4); CCDC1851708: non cubic form of (dipPhO)8PcCu (Supplementary Table 4); CCDC1853490: PNC[cC60/Co–vPy] (Supplementary Table 5) CCDC1856443: non-cubic form of (dipPhO)8PcAg (Supplementary Table 5); CCDC1857087: PUNC[cC60/Co] desolvated by stream of nitrogen at room temperature (Supplementary Table 5); CCDC1851749–1851759: PNC[cC60/Co–vH2O] high-pressure compression study (Supplementary Table 7); CCDC185729–1851735: PNC[cC70/Co–vH2O] high-pressure compression study (Supplementary Table 8); CCDC1851743–1851745: PNC[Co–cbipy–Co] high-pressure compression study (Supplementary Table 9); CCDC1851736–1851742: structures of PUNC[cC60/Co] from gas cell experiments including structure evacuated in vacuum and subjected up to 8.5 bar of CO (Supplementary Table 11); CCDC1851416–1851422: structures of PUNC[cC60/Co] from gas cell experiments including structure evacuated in vacuum and subjected up to 8.5 bar of O2 (Supplementary Table 12); CCDC1851746: PUNC[cC60/Cu] desolvated by application of vacuum in gas cell (Supplementary Table 13); CCDC1851747: PUNC[cC60/Ag] desolvated by application of vacuum in gas cell (Supplementary Table 13); CCDC1851748: PUNC[cC60/H2] desolvated by application of vacuum in gas cell (Supplementary Table 13).
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We thank the EPSRC via grant EP/N01331X/1 and the University of Edinburgh for funding and the Diamond Light Source for beamtime on Station I19.
The authors declare no competing interests.
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Bezzu, C.G., Burt, L.A., McMonagle, C.J. et al. Highly stable fullerene-based porous molecular crystals with open metal sites. Nat. Mater. 18, 740–745 (2019). https://doi.org/10.1038/s41563-019-0361-0
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