| 摘要註: |
首先，由3,6-di-tert-butyl-9H-carbazole(1)直接以Friedel-Crafts acylation的方式合成出1,8-di-acetyl-3,6-di-tert-butyl-9H-carbazole(2)，並以三氯化鋁的當量數以及加入反應試劑的順序探討咔唑上進行Friedel-Crafts acylation的反應途徑，再找到適合化合物2進行去烷基化的反應條件，且可得到化合物2進行去烷基化的產物1,8-di-acetyl-9H-carbazole(4)，化合物2、4並於甲苯溶液中與一級胺進行縮合反應，得到一系列NNN型的三芽、單陰離子之螯型配位基(5-10)，化合物2,4-7,8-10均以1H NMR、13C NMR鑑定，而化合物6,8及10再以X-ray單晶繞射儀鑑定其固態結構。一系列雙亞胺配位基與鋁或鎳形成二乙基鋁金屬錯化合物(5a-10a)、二氯鋁金屬錯化合物(5b-10b)及鎳金屬錯化合物(5c-10c)，金屬錯化合物同樣也以1H NMR、13C NMR或元素分析鑑定之，但由於鎳二價金屬中心具有順磁性的特性，我們又以二維核磁共振光譜（2D Homo-COSY）、同核去耦合光譜（Homo-nuclear decoupling）作更進一步的鑑定，而金屬錯化合物5a-7a與9c也以X-ray單晶繞射儀鑑定其固態結構。 藉由物性與化性的探討，我們亦發現咔唑3,6號位置的取代基對於整體的電子效應影響較小，而配位基到二乙基鋁金屬錯化合物時，在吸收光譜上會有紅位移的現象發生，且從二乙基鋁金屬錯化合物改變為二氯鋁金屬錯化合物時，放光的強度會增強且放光波長在可見光區內(496-498nm)；至於催化活性方面，我們利用二乙基鋁金屬錯化合物(5a-10a)或鎳金屬錯化合物(5c-10c)進行催化methyl methacrylate(MMA)的聚合反應，得到有1,8-bis(n-hexylimino)-3,6-di-tert-butyl-carbazolide]-Al(CH2CH3)2 (6a)和[1,8-bis(n-hexylimino)-carbazolide]-Al(CH2CH3)2 (9a)有較好的催化結果，可能是因為雙亞胺基上的取代基有較小的立體障礙，使得其催化性能較佳，而鎳金屬錯化合物不具有任何的催化活性，則可能是因為受到配位基對於金屬中心的立體障礙過大，造成無法形成有效的陽離子金屬中心，進而進行催化聚合的反應。 The convenient synthesis of 1,8-di-acetyl-3,6-di-tert-butyl-9H-carbazole(2) has been developed through the direct Friedel-Crafts acylation with 3,6-di-tert-butyl-9H-carbazole(1), and a variety of AlCl3 equivalents and experimental methods (A-E) are used for studying mechanism of acylation on (1). The synthesis of dealkylation with (2) is found, for a new 1,8-disubstituted-carbazole as 1,8-di-acetyl-9H-carbazole(4). A series of tridentate, mono-anionic NNN-pincer type 1,8-bis(aryl or alkylimino)carbazole ligands(5-10) are prepared by condensation (2) and (4) with primary amine in toluene. The ligands are fully characterized by EA, 1H NMR and 13C NMR. And a variety of metal complexes bearing 1,8-bis(imino)carbazolide ligand are synthesized such as diethylaluminum (5a-10a), dichloroaluminum(5b-10b) or Ni(Ⅱ) complexes(5c-10c). The metal complexes are also characterized by EA, 1H NMR and 13C NMR,moreover Ni(Ⅱ) complexes are characterized further by 2D-COSY or homo-nuclear decoupling. The solid-state structures of some ligands and metal complexes are characterized by x-ray diffraction crystallography.The luminescent properties of all compounds and complexes have been studied. The change from ligands to aluminum complexes cause a red-shift of the absorption bands, and increase the photoluminescence intensity with dicholoroaluminum complexes. All the dichloroaluminum complexes show emission at visible region(468-498nm). The catalytic polymerization of diethylaluminum(5a-10a) and Ni(5c-10c) complexes under coordination polymerization process have been studied. The 1,8-bis(n-hexylimino)-3,6-di-tert-butyl-carbazolide]-Al(CH2CH3)2 (6a) and [1,8-bis(n-hexylimino)-carbazolide]-Al(CH2CH3)2 (9a)show the better catalytic results because of the less steric effect on the metal center. And the Ni complexes didn’t show any polymerization result with Et3Al, NaSbF6 or AgBF4 as cocatalyst. Because of their steric effect with bulky ligand stabilize the metal center leading to the metal complexes have no activity in polymerization. |