Flexibility Control of Two-Dimensional Coordination Polymers by Crystal Morphology: Water Adsorption and Thermal Expansion

Ryo Ohtani; Haruka Yoshino; Junichi Yanagisawa; Hiroyoshi Ohtsu; Daisuke Hashizume; Yuh Hijikata; Jenny Pirillo; Masaaki Sadakiyo; Kenichi Kato; Yuta Shudo; Shinya Hayami; Benjamin Le Ouay; Masaaki Ohba

doi:10.1002/chem.202103404

Flexibility Control of Two-Dimensional Coordination Polymers by Crystal Morphology: Water Adsorption and Thermal Expansion

Chemistry. 2021 Dec 23;27(72):18135-18140. doi: 10.1002/chem.202103404. Epub 2021 Nov 24.

Authors

Affiliations

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.

PMID: 34741369
DOI: 10.1002/chem.202103404

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)]₂ [ReN(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: coordination polymers; crystal morphology; metal-organic frameworks; thermal expansion; water adsorption.

Abstract

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