| Summary: | 碩士 === 國立暨南國際大學 === 應用化學系 === 94 === The goal of this thesis is to develop self-assembly synthetic strategy to prepare metal-organic supramolecules and coordination polymers by using piperazine derivatives i.e. 4,4'-dipyridylpiperazine (2N-DPyP) and N-N'-ipyraziylpiperazine (4N-DPzP) as flexible ligands.
In the aspect of discrete cyclic supramolecules, reaction of 2N-DPyP with Re2(CO)10 in the presence of methanol or dithiol under hydrothermal conditions gave compounds [Re4(CO)12 (2N-DPyP) (OCH3)4] (1) and [Re4(CO)12 (2N-DPyP) (SCH3)4] (2), respectively. Compounds 1 and 2 adopt rectangular architecture. Treatment of Re2(CO)10, 2N-DPyP and naphthoquinone or benzo-imidazole affoded triangular complexes {[Re2(CO)6 (2N-DPyP) (C10H4O4)]‧(C7H8)} (3) and{[Re2(CO)6(2N-DPyP) (C14H8N4)]‧(C9H12)2.5} (4), respectively. The conversion of chair form of piperazine derivative to boat form was observed during the self-assembly process, leading to the formation of triangular products.
Reaction of Re2(CO)10 with 4N-DPzP in butanol under hydrothermal conditions produced 1D compound [Re2(CO)6(4N-DPzP) (OC4H9)2 ]n (5). Treatment of 4N-DPzP with Cd(ClO4)2．H2O or silver salts at ambient temperature yielded 1D polymers [Cd (4N-DPzP)3(ClO4)2]n (6), {[Ag(4N-DPzP)]( SbF6)}n (7), {[Ag(4N-DPzP)](ClO4)}n (8) and{[Ag(4N-DPzP)]( PF6)}n (9), respectively.
The products were characterized by spectroscopic methods, and their structures were further confirmed by single-crystal diffraction analysis.
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