| Summary: | 碩士 === 國立勤益科技大學 === 化工與材料工程系 === 97 === Professor Jean-Marie Lehn reported the tendency toward a field of supramolecular chemistry, and studied organic molecular structure of covalent link between atoms (called molecular chemistry). Supramolecular chemistry is further developed to study the supramolecular architectures via non-covalence interaction between molecules, and further, studying covalence and non-covalence interaction of molecular structure that may form and break reversibly. Therefore it is called constitutional dynamic chemistry (CDC). In this thesis, we study on supramolecular materials and molecular switching materials via weak-link approach, and these involve in dynamic transform. We design and synthesize four kinds of flexible hemilabile diaminodiamide ligands that are N,N’-bis (β- carbamoylethyl)1,2-diaminocyclohexane (BDC), 4,7-diazadecanedi- amide (L-2,2,2), 4,8-diazaundecanediamide (L-2,3,2) and 4,7-dimethyl- 4,7-diazadecanediamide (4,7-Me2-L-2,2,2), respectively. We utilize these ligands with transition metal ions (Co2+, Ni2+, Cu2+) to coordinate and self-assemble to generate supramolecular materials, and further, studying molecular switching and strategy of the weak-link approach to synthesize supramolecular materials.
To the research of the molecular switching , we use flexible hemilabile BDC ligand with transition metal ions (Cu2+, Ni2+) to yield compounds 1 and 2, and these compound were reorganized in basic solution, resulting in compounds 3 and 4. The structures can be reversible in acid and basic solution. Compounds 1 and 2 can change as the L/M2+ concentration ratio in solution to form compounds 5 and 6, respectively. The structures are the same as compounds 3 and 4.
To the research of the strategy of the weak-link approach to synthesize supramolecular materials, we utilize flexible hemilabile BDC and L-2,2,2 ligands with transition metal ions (Cu2+, Ni2+) to form a precursor via coordination, then added into a ancillary ligand (1,2-diamineocyclohexane, 2,2’-bipyridine, 4,4’-bipyridine). Finally, we yield substitution reaction products compound 7, enantiomer compound 8 and supramolecular polymer compound 9 in this strategy.
In the end, we utilize different transition metal ions (Co2+, Ni2+, Cu2+,) with flexible hemilabile L-2,2,2 and L-2,3,2 to yield compounds 10-15, respectively, and then study these compounds’ structure and physical property.
These compounds were structurally characterized by elemental analyzer, Fourier Transform Infrared spectrometer and single-crystal X-ray diffraction method. Thermal stabilities were studies by thermogravimetric analyzer. Electronic spectra behaviors were studies by UV/Vis spectrophotometer.
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