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

International Journal of Molecular Sciences

Mitsuru Kondo³  Hideaki Takahashi¹  Hirotaka Watanabe¹  Yusuke Shimizu¹  Katsunori Yamanishi¹  Makoto Miyazawa¹  Naoko Nishina¹  Yutaka Ishida²  Hiroyuki Kawaguchi² 

[1] Department of Chemistry, Faculty of Science, Shizuoka University, 836 Ohya, Suruga-kul, Shizuoka 422-8529, Japan; E-Mail:;Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan; E-Mails:;Center for Instrumental Analysis, Shizuoka University, 836 Ohya, Suruga-kul, Shizuoka 422-8529, Japan

关键词: porous coordination networks;    phase transition;    dynamic structural change;    crystal structure;   

DOI  :  10.3390/ijms11082821

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2010 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland.