| Summary: | 碩士 === 國立臺灣科技大學 === 化學工程系 === 104 === This thesis is comprised of two parts. The first part describes the preparation of the complexes {[Re(CO)3]2(dhaq)(bpmpa)} (1, dhaq = 1,4-dihydroxy-9,10- anthraquinone, bpmpa = N,N′-Bis(pyridin-4-ylmethyl)-1,4-phenylenediamine) and {[Re(CO)3]2(dhnq)(bpmpa)} (2, dhnq = 6,11-dihydroxy-5,12-naphthacenedione) by treating Re2(CO)10 with bpmpa and H2dhaq or H2dhnq, respectively, under solvothermal conditions. Rhenium-based complexes 1 and 2 were characterized using FT-IR, 1H NMR, FAB-MS spectroscopic techniques, elemental analysis, UV–visible spectroscopy and fluorescence spectrometry. The structures of complexes 1 and 2 were further confirmed by single-crystal X-ray diffraction analysis. The para-phenylene group of the coordinated bpmpa ligand in complexes 1 or 2 rotate in solution at ambient temperature. The activation energy for the rotation of complex 2 was calculated to be 10.3 kcal/mol based on dynamic 1H NMR spectroscopic data.
The second part reports on the successful synthesis of the complexes {{[Re(CO)3]2(dhnq)}2(1,4-bpeb)2}·2[C6H3(CH3)3] (3, 1,4-bpeb = 1,4-Bis[2-(4-pyridyl) ethenyl]benzene), {{[(Re(CO)3]2BIm}2(1,4-bpeb)2}·2(C4H8O) (4, BIm = 2,2’-Biimidazole) and {{[Re(CO)3]2BIBzIm}2 (1,4-bpeb)2}·2[C6H4(CH3)2] (5, BiBzIm = 2,2’-Bisbenzimidazole) by treating Re2(CO)10 with 1,4-bpeb and H2dhnq, BImH2 or BiBzImH2. Complexes {{[(Re(CO)3)2BIm}2 (1,6-bpht)2}·2(C4H8O) (6, 1,6-bpht = trans,trans,trans-1,6-Bis(4-pyridyl)-1,3,5-hexatriene) and {{[Re(CO)3]2 BIBzIm}2(1,6-bpht)2}·2(C7H8) (7) were also successfully synthesized by treating Re2(CO)10 with 1,6-bpht and BImH2 or BiBzImH2, respectively, under solvothermal conditions. The complexes 37 were characterized using FT-1R, 1H NMR, FAB-MS spectroscopic techniques and elemental Analyses. The structures were further confirmed by single-crystal X-ray diffraction analysis. In the solid state, complexes 47 participated in interesting [2+2] cycloaddition reactions of the adjacent triene moieties upon irradiation with visible light. The cycloaddition products were characterized by 1H NMR, UV-visible spectrometry and fluorescence spectrometry. In addition, complexes 47 were also found to undergo cycloaddition reactions in the liquid state as a result of irradiation with light. The presence of substituents having electron-withdrawing effects on the bisimidazolate appear to affect the cycloaddition reactions.
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