Structural Transformation and Luminescent Properties of Zn(II) and Cd(II) Based Coordination Frameworks Containing Dipyridylamide Ligands

• Main Authors: Wei, Sheng Luen, 魏聖倫
• Other Authors: Tzeng, Biing-Chiau
• Format: Others
• Language: zh-TW
• Published: 2011
• Online Access: http://ndltd.ncl.edu.tw/handle/74169637815152069929

碩士 === 國立中正大學 === 化學暨生物化學研究所 === 99 === We used a series of dipyridylamide ligands, N,N’-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (papc)、N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl ether (papo) and N,N'-bis(pyridylcarbonyl)-4,4'-diaminodiphenyl thioether (paps), to react with Zn(ClO4)2 and Cd(ClO4)2 respectively to give two-dimensional (2-D) polyrotaxane (PR) frameworks, [Zn(papc)2(ClO4)2]n (1)、[Cd(papc)2(ClO4)2]n (3), and one-dimensional double-zigzag (DZ) frameworks, {[Zn(papc)2(H2O)2](ClO4)2．CH3OH }n (2)、{[Cd(papc)2(H2O)2](ClO4)4．CH3OH．CHCl3}n (4)、{[Cd(papo)2(H2O)2](ClO4)2}n (5) and {[Cd(paps)2(H2O)2](ClO4)2}n (6), in the different reaction conditions. The difference in the formation of PR and DZ structures relies on the fact that water coordinates to the Zn(II) and Cd(II)ion in the DZ structures, but ClO4- coordination instead is found in the PR structure. Interestingly, 2, 4, 5, and 6 were demonstrated to show phase transformation properties from DZ to PR by heating and only 5 can be recovered by grinding in the presence of water. The interesting and novel structural transformation can be proven experimentally by powder and single-crystal X-ray diffraction studies. Moreover, this remarkable mechanochromism in the transformation process is also observed by monitoring their luminescence images.