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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

1,2,* , 2
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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 which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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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