Crystalline coordination framework endowed with dynamic gate-opening behaviour by being downsized to a thin film

Shun Sakaida; Kazuya Otsubo; Osami Sakata; Chulho Song; Akihiko Fujiwara; Masaki Takata; Hiroshi Kitagawa

doi:10.1038/nchem.2469

Crystalline coordination framework endowed with dynamic gate-opening behaviour by being downsized to a thin film

Shun Sakaida, Kazuya Otsubo, Osami Sakata, Chulho Song, Akihiko Fujiwara, Masaki Takata, Hiroshi Kitagawa

SRIS - SR Core Research Division

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183 Citations (Scopus)

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.

Original language	English
Pages (from-to)	377-383
Number of pages	7
Journal	Nature Chemistry
Volume	8
Issue number	4
DOIs	https://doi.org/10.1038/nchem.2469
Publication status	Published - 2016 Apr 1

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title = "Crystalline coordination framework endowed with dynamic gate-opening behaviour by being downsized to a thin film",

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.",

author = "Shun Sakaida and Kazuya Otsubo and Osami Sakata and Chulho Song and Akihiko Fujiwara and Masaki Takata and Hiroshi Kitagawa",

note = "Funding Information: 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). Publisher Copyright: {\textcopyright} 2016 Macmillan Publishers Limited. All rights reserved.",

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AU - Sakaida, Shun

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AU - Sakata, Osami

AU - Song, Chulho

AU - Fujiwara, Akihiko

AU - Takata, Masaki

AU - Kitagawa, Hiroshi

N1 - Funding Information: 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). Publisher Copyright: © 2016 Macmillan Publishers Limited. All rights reserved.

PY - 2016/4/1

Y1 - 2016/4/1

N2 - 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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Crystalline coordination framework endowed with dynamic gate-opening behaviour by being downsized to a thin film

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