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

Crystal structures and dynamic rearrangements of one-dimensional coordination polymers with 4,4′-dipyridylsulfide (dps) have been studied. Reaction of Ni(NO(3))(2)·6H(2)O with dps in EtOH yielded [Ni(dps)(2)(NO(3))(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)(NO(3))(2)] (2a), which was also obtained by treatment of Ni(NO(3))(2)·6H(2)O 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)(NO(3))(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(NO(3))(2)·6H(2)O with dps in acetone provided [Ni(dps)(NO(3))(2)(H(2)O)] ·Me(2)CO (4) with no channel structure. When MeOH or acetone was used as a reaction solvent, the [Ni(dps)(2)(NO(3))(2)] · (guest molecule) type coordination polymer, which was observed in 1, was not formed. Nevertheless, the reaction of Ni(NO(3))(2)·6H(2)O with dps in MeOH/acetone mixed solution produced [Ni(dps)(2)(NO(3))(2)]·0.5(MeOH·acetone) (5), which has an isostructural Ni-dps framework to 1.