Abstract
The fabrication of porous coordination frameworks in thin-film forms has been investigated intensively with a view to using their structural response to external stimuli and guests for potential nanotechnological applications, for example as membranes for gas separation. Here we report a coordination framework that exhibits a dynamic guest-sorption behaviour in a nanometre-sized thin-film form (16 nm thick), yet shows no guest uptake in the bulk. Highly oriented crystalline thin films of this coordination framework—which consists of interdigitated two-dimensional layers of {Fe(py)2[Pt(CN)4]} (py, pyridine)—were fabricated through liquid-phase layer-by-layer synthesis. The resulting thin film exhibited a clear guest uptake with a structural transformation of the gate-opening type as characterized by in situ X-ray diffraction. Increasing the film's thickness markedly suppressed this behaviour. We envisage that such a crystal-downsizing effect may be observed with other coordination frameworks, and may be of use to develop functional materials, for example, for switching or sensing devices.
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Acknowledgements
This work was partly supported by Grants-in-Aid for Scientific Research (A) (Grant No. 20350030 and 23245012) and Grant-in-Aid for Young Scientists (B) (Grant No. 25810039) from the Japan Society for the Promotion of Science. Synchrotron XRD measurements were supported by JASRI (Proposal No. 2010B1468, 2011A1382, 2011A1463, 2011B1013, 2011B1529, 2012A1505, 2012A1508, 2012B1518, 2012B1304, 2013A1146, 2013A1486 and 2013B1410).
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K.O. and H.K. conceived the work and designed this study. S.S., K.O. and C.S. performed the experiments. O.S., C.S., A.F. and M.T. contributed to the synchrotron XRD measurements. S.S., K.O. and H.K. co-wrote the manuscript. All the authors discussed and commented on the paper.
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Sakaida, S., Otsubo, K., Sakata, O. et al. Crystalline coordination framework endowed with dynamic gate-opening behaviour by being downsized to a thin film. Nature Chem 8, 377–383 (2016). https://doi.org/10.1038/nchem.2469
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DOI: https://doi.org/10.1038/nchem.2469
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