含三雙硫鍵連接籠子型式接受子對中性分子的辨識與包覆探討

Autor: 郭志宏
Rok vydání: 2010
Druh dokumentu: 學位論文 ; thesis
Popis: 98
For the development of functional molecules such as molecular receptors and metal ligands in the fields of molecular recognition chemistry and supramolecular chemistry, the 1,3,5-triethylbenzene derivatives have attracted much attention as efficient building blocks due to their rigid pre-organized facial architectures. Previously, we succeeded in synthesizing and characterizing 1,3,5-triethylbenzene derivatives, 1,3,5-triethyl-2,4,6-tris(2-mercaptoanilinyl[1]methyl)benzene (trithiol), and its disulfide bond crossed-linked molecule (cage). Herein, the recognition and encapsulation of neutral molecules, such as MeI, I2, CHCl3, CH3CN, CH3NO2, and MeOH, by cage molecule were investigated by variable-temperature 1H-NMR studies and structural analyses. Cage molecule is hardly soluble in most of solvents, but remarkable soluble in benzene and toluene. In order to make good use of cage for greater biological relevance, we tried to make its derivatives. The derivatives should maintain the core building block. At the same time, the derivative should be more soluble in most of solvents. However, the attempts to synthesize two derivatives of cage were not successful in this report. The ethyl groups substituted by H groups or 2-aminothiophenol moieties substituted by 2-hydroxythiophenol moieties all results in polymerization products instead of cage molecules. In addition, we also tried to isolate mononuclear nickel complex from trinuclear Ni2+ compound (Tri-Ni) using monodentate ligand, such as CN- to dissociate the trinuclear metal complex. We were hoping to synthesize the coordination-unsaturated nickel compound, which are expected to have more catalytic activity for several kinds of reactions.
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