含亞胺基苯並三唑苯酚氧基之鋅錯合物合成、結構鑑定、光性質與二氧化碳/環氧化合物偶合反應

Zinc complexes supported by imine-benzotriazole phenoxide ligands: Synthesis, characterization, photoluminescent properties and catalysis for CO2/epoxide coupling reaction

陳庭懿(Ting-Yi Chen)

指導教授 ： 柯寶燦

中原大學/理學院/化學研究所/碩士(2012年)

https://doi.org/10.6840/cycu201200217

摘要

本論文利用Duff reaction，將苯並三唑苯酚(benzotriazole phenol，BTP-H)，形成有醛官能基的配位基C1AldBTP-H、C8AldBTP-H，接著與2-methoxyethylamine和 furfurylamine這兩種一級胺，經imination形成含亞胺之四芽的配位基C1NOIBTP-H(A)、C8NOIBTP-H(B)、C1FuIBTP-H(C)、C8FuIBTP-H(D)。將上述配位基與二乙基鋅在2：1的條件下，成功取得空氣穩定的雙取代錯合物(1)-(4)。經由1H NMR、13C NMR、元素分析以及X-ray單晶繞射儀鑑定來證明結構。
將錯合物(1)-(4)與助催化劑(NnBu4Br)分別與二氧化碳及環氧丙烷在溫和的反應條件下(50oC, 150 psi)進行偶合反應。由實驗結果顯示，以錯合物[(C8FuIBTP)2Zn](4)有較佳的催化活性，可能是因為個錯合物對二氧化碳的溶解度效果有些微的差異造成此結果的產生。選用與二氧化碳及環氧丙烷偶合反應效果最佳之錯合物(4)，並將其單體改變為氧化苯乙烯或助催化劑改為DMAP，也可得到催化效果，並推測可能之反應機制。
由於本論文合成之錯合物(1)-(4)為空氣穩定的錯合物，利用可見光-紫外光光譜儀及螢光光譜儀測量其吸收波長、放光波長與量子產率。實驗結果顯是個錯合物的放光波長約為470~480 nm的範圍，量子產率約20%至24%。並將錯合物(1)-(4)配位上中性化合物DMAP (5)-(8)及imidazole (9)-(12)，可發現錯合物(5)-(8)量子產率並無明顯提升。此外，因imidazole為一有放光性質之化合物，因此錯合物(9)-(12)量子產率提高約3%。

關鍵字

環氧化合物 ； 偶合反應 ； 二氧化碳 ； 量子產率 ； 亞胺 ； 光性質 ； 鋅

並列摘要

Four imine-benzotriazole phenoxide ligands, C1NOIBTP-H (1); C8NOIBTP-H (2); C1FUIBTP-H (3); C8FUIBTP-H (4) were prepared from the condensation of 3-(2H-benzotriazol-2-yl)-2-hydroxy-5-alkyl-benzaldehyde (alkyl = CH3 and C8H17) with the 2-methoxyethanamine or 1-(2-furyl)methylamine (1.1 equiv) in ether. A series of monomeric tetra-coordinated zinc complexes supported by imine- benzotriazole phenoxide ligands were synthesized and fully characterized. The homoleptic and monomeric complexes [(RIBTP)2Zn] (R = C1NO (A); R = C8NO (B); R = C1FU (C) and R = C8FU (D)) result from treatment of RIBTP-H (2.0 equiv) with ZnEt2, in which the metal center is four-coordinated by two N,O-bidentate RIBTP- ligands. Optical properties and catalysis for epoxide with carbon dioxide coupling reaction of Zn complexes are studied. Luminescent properties of complexes 1-4 in solution were studied, and it was found that maxima emission wavelength (lmax) of 1-4 are in the range 470-480 nm and quantum yield are 20%-24%, depending on the substituents on the imino of their ligands. Interestingly, when complexes coordination different netural co-ligand, 3% of quantum yield would be uncreased. The coupling reaction of CO2 with propylene oxide (PO) catalyzed by air-stable Zn complexes 1-4 in the presence of quaternary ammonium salts (n-Bu4NX) to produce propylene carbonate (PC) was systematic investigated under mild conditions.

並列關鍵字

coupling ； zinc ； photoluminescent ； quantum yield ； carbon dioxide ； Schiff base ； imine

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