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Int. J. Mol. Sci. 2010, 11(8), 2821-2838; doi:10.3390/ijms11082821
Article

Syntheses and Characterization of New Nickel Coordination Polymers with 4,4’-Dipyridylsulfide. Dynamic Rearrangements of One-Dimensional Chains Responding to External Stimuli: Temperature Variation and Guest Releases/Re-Inclusions

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1 Center for Instrumental Analysis, Shizuoka University, 836 Ohya, Suruga-kul, Shizuoka 422-8529, Japan 2 Department of Chemistry, Faculty of Science, Shizuoka University, 836 Ohya, Suruga-kul, Shizuoka 422-8529, Japan 3 Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan 4 Hautform Division, Fuji Chemical Co. Ltd. 1683-1880, Nakagaito, Nasubigawa, Nakatsugawa, Gifu 509-9132, Japan
* Author to whom correspondence should be addressed.
Received: 10 June 2010 / Revised: 13 July 2010 / Accepted: 15 July 2010 / Published: 2 August 2010
(This article belongs to the Special Issue Metal Organic Frameworks)
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Abstract

Crystal structures and dynamic rearrangements of one-dimensional coordination polymers with 4,4'-dipyridylsulfide (dps) have been studied. Reaction of Ni(NO3)2·6H2O with dps in EtOH yielded [Ni(dps)2(NO3)2]·EtOH (1), which had channels filled with guest EtOH molecules among the four Ni(dps)2 chains. This coordination polymer reversibly transformed the channel structure responding to temperature variations. Immersion of 1 in m-xylene released guest EtOH molecules to yield a guest-free coordination polymer [Ni(dps)2(NO3)2] (2a), which was also obtained by treatment of Ni(NO3)2·6H2O with dps in MeOH. On the other hand, removal of the guest molecules from 1 upon heating at 130 °C under reduced pressure produced a guest-free coordination polymer [Ni(dps)2(NO3)2] (2b). Although the 2a and 2b guest-free coordination polymers have the same formula, they showed differences in the assembled structures of the one-dimensional chains. Exposure of 2b to EtOH vapor reproduced 1, while 2a did not convert to 1 in a similar reaction. Reaction of Ni(NO3)2·6H2O with dps in acetone provided [Ni(dps)(NO3)2(H2O)]·Me2CO (4) with no channel structure. When MeOH or acetone was used as a reaction solvent, the [Ni(dps)2(NO3)2]·(guest molecule) type coordination polymer ,which was observed in 1, was not formed. Nevertheless, the reaction of Ni(NO3)2·6H2O with dps in MeOH/acetone mixed solution produced [Ni(dps)2(NO3)2]·0.5(MeOH·acetone) (5), which has an isostructural Ni-dps framework to 1.
Keywords: porous coordination networks; phase transition; dynamic structural change; crystal structure porous coordination networks; phase transition; dynamic structural change; crystal structure
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).
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Kondo, M.; Takahashi, H.; Watanabe, H.; Shimizu, Y.; Yamanishi, K.; Miyazawa, M.; Nishina, N.; Ishida, Y.; Kawaguchi, H.; Uchida, F. Syntheses and Characterization of New Nickel Coordination Polymers with 4,4’-Dipyridylsulfide. Dynamic Rearrangements of One-Dimensional Chains Responding to External Stimuli: Temperature Variation and Guest Releases/Re-Inclusions. Int. J. Mol. Sci. 2010, 11, 2821-2838.

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