| Summary: | 碩士 === 國立中正大學 === 化學暨生物化學研究所 === 101 === We used a series of dipyridylamide ligands, N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl thioether (paps)、 N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl ether (papo) and N,N’-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (papc), to react with Co(II)、Ni(II) and Cu(II) respectively to give one-dimensional double-zigzag (DZ) frameworks, {[Co(paps)2(H2O)2](ClO4)2(H2O)2}n (1)、{[Co(papo)2(H2O)2](ClO4)2(H2O)2}n (2)、{[Co(papc)2(H2O)2](ClO4)2(H2O)2(C7H8)}n (3)、{[Ni(paps)2(H2O)2](ClO4)2(H2O)2}n (4)、{[Ni(papo)2(H2O)2](ClO4)2(H2O)2}n (5), and two-dimensional polyrotaxane (PR) frameworks, [Cu(paps)2(ClO4)2] (6), in the different reaction conditions. This difference relies on the fact that water coordinates to the center ion in double-zigzag frameworks , but anions coordination is found in polyrotaxane frameworks. Although [Cu(papo)2(ClO4)2] (7) and [Cu(papc)2(ClO4)2] (8) can not get its crystal structure successfully, but still can identify by powder X-ray diffraction.
Interestingly, 1, 2, 4 and 5 were demonstrated to show phase transformation properties from double-zigzag frameworks to polyrotaxane frameworks by heating and grinding in the presence of moisture, and such a structural transformation can also be proven experimentally by powder X-ray diffraction studies. However, 3, 6, 7 and 8 cannot perform such a reversible cycle. Compound 3 is due to the steric effect of papc as the related to Zn(II) complexes. By replacing the above metal ions with Cu(II), the irreversible phase transformation has been observed, and thus is most likely ascribed to the Jahn-Teller effect of Cu(II).
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