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Flexibility Control of Two-Dimensional Coordination Polymers by Crystal Morphology: Water Adsorption and Thermal Expansion |
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| Authors: | Prof Ryo Ohtani Dr Haruka Yoshino Junichi Yanagisawa Dr Hiroyoshi Ohtsu Dr Daisuke Hashizume Prof Yuh Hijikata Dr Jenny Pirillo Prof Masaaki Sadakiyo Dr Kenichi Kato Dr Yuta Shudo Prof Shinya Hayami Dr Benjamin Le Ouay Prof Masaaki Ohba |
| Institution: | 1. Department of Chemistry, Faculty of Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395 Japan;2. Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8550 Japan;3. RIKEN Center for Emergent Matter Science (CEMS), 2-1, Hirosa-wa, Wako-shi, Saitama, 351-0198 Japan;4. Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, 001-0021 Japan;5. Department of Applied Chemistry, Faculty of Science Division I, Tokyo University of Science, Kagurazaka 1–3, Shinjuku-ku, Tokyo, 162-8601 Japan;6. RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5148 Japan;7. Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto, 860-8555 Japan |
| Abstract: | Layer flexibility in two-dimensional coordination polymers (2D-CPs) contributes to several functional materials as it results in anisotropic structural response to external stimuli. Chemical modification is a common technique for modifying layer structures. This study demonstrates that crystal morphology of a cyanide-bridged 2D-CP of type Mn(salen)]2ReN(CN)4] ( 1 ) consisting of flexible undulating layers significantly impacts the layer configuration and assembly. Nanoplates of 1 showed an in-plane contraction of layers with a longer interlayer distance compared to the micrometer-sized rod-type particles. These effects by crystal morphology on the structure of the 2D-CP impacted the structural flexibility, resulting in dual-functional changes: the enhancement of the sensitivity of structural transformation to water adsorption and modification of anisotropic thermal expansion of 1 . Moreover, the nanoplates incorporated new adsorption sites within the layers, resulting in the uptake of an additional water molecule compared to the micrometer-sized rods. |
| Keywords: | crystal morphology coordination polymers metal-organic frameworks thermal expansion water adsorption |