中 文 摘 要
本研究以2-胺基苯甲醛 (2-aminobenzaldehyde) 、2-胺基苯甲酮(2-aminoacetophenone)、2-胺基苯甲酸 (2-aminobenzoic acid) 為主要配子，合成了十六環四牙基錯合物與十二環三牙基錯合物，十六環四牙基錯合物有[Cu(TAAB)](NO3)2、[Cu(TAAB)](BF4)2、[Fe(TAAB)](FeCl4)；十二環三牙基錯合物有[Cu(TRI)(CH3CN)](CF3SO3)、[Ni(TRI)(H2O)2(NO3)](NO3)、[Cu(TRI)(CH3CN)](BF4)、[Co(TRI)(H2O)](NO3)2、[Cu(TRI-OCH3)(CH3CN)](CF3SO3)、[Cu(TRI)2](BF4)2.H2O、[Cu(TRI-Me3)]2O2(BF4)2.7H2O、[Cu(C21H14N3O3-)]2O2.6H2O.CH3CN、[Cu(C27H26N3O9-)]2O2.3H2O。利用元素分析、紅外光光譜、紫外光-可見光吸收光譜、質譜儀、電子順磁共振光譜及X-光單晶結構解析等方法，完成錯合物的結構鑑定及鍵結性質之探討。
目前已有X-光單晶結構解析的錯合物有：
1. [Cu(TAAB)](CF3SO3)2
屬於三斜晶系（triclinic），空間群為P，晶格常數a = 7.991(2) Å，b = 13.877(3)Å，c = 15.98(1)Å，α = 114.46(3)∘，β = 97.9(3)∘，γ = 102.52(2)∘，每單位晶格內含有2個分子（Z = 2），精算值 R = 0.134，RW = 0.149。
2. [Cu(TAAB)](BF4)2
屬於單斜晶系（monoclinic），空間群為P21/n，晶格常數a = 11.830 (2) Å，b = 13.380(2)Å，c = 16.737(3)Å，β = 92.82(2)∘，每單位晶格內含有4個分子（Z = 4），精算值 R = 0.086，RW = 0.085。
由X-光單晶結構解析可得知：兩個具有共軛雙鍵系統十六環四牙基的錯合物，因陰離子大小不同，造成結構上的不同，一個接近雙三角錐形體，另一個為四角錐形體。另外合成出來的具有共軛雙鍵系統三牙基錯合物：[Cu(TRI)(CH3CN)](CF3SO3)、[Cu(TRI)(CH3CN)](BF4)、[Cu(CH3O-TRI)(CH3CN)](CF3SO3)，進行通氧實驗，從電子光譜判斷推論此過氧化物符合m-h2：h2-peroxo鍵結模式，顯示得到室溫下存在的血青素模型錯合物。而由 2-胺基苯甲酸(2-aminobenzoic acid)與一價銅的錯合物與氧反應，從電子光譜來判斷，亦形成m-h2：h2-peroxo的錯合物。

Abstract
This study deals with macrocyclic coordnation compounds formed by the metal-templated self-condensation reactions of 2-aminobenzaldehyde and its derivatives. The complexes，which include [Cu(TAAB)](NO3)2 , [Cu(TAAB)](BF4)2 , [Fe(TAAB)]-FeCl4 , [Cu(TRI)(CH3CN)](CF3SO3) , [Ni(TRI)(H2O)2(NO3)](NO3) , [Cu(TRI)(CH3CN)](BF4) , [Co(TRI)(H2O)](NO3)2 , [Cu(TRI-OCH3)(CH3CN)](CF3SO3) , [Cu(TRI)2](BF4)2.H2O , [Cu(TRI-Me3)]2O2(BF4)2.7H2O，[Cu(C21H14N3O3-)]2O2.6H2O.CH3CN and [Cu(C27H26N3O9-)]2O2.3H2O, have been prepared by several synthetic approaches，and characterized by elemental analyses , infrared , electronic , mass and epr spectroscopic measurements .
By using single-crystal X-ray diffraction method , the crystal and molecular structures of [Cu(TAAB)](CF3SO3)2 and [Cu(TAAB)](BF4)2 have been determined . Their crystal data are described below :
1. [Cu(TAAB)](CF3SO3)2 crystallizes in the triclinic , space group Pwith a = 7.991(2) Å , b = 13.877(3)Å , c = 15.98(1)Å , α = 114.46(3)∘, β = 97.9(3)∘, γ = 102.52(2)∘, Z = 2 , R = 0.134 and RW = 0.149 .
2. [Cu(TAAB)](BF4)2 crystallize in the monoclinic , space group P21/n with a = 11.830 (2) Å , b = 13.380(2)Å , c = 16.737(3)Å , β = 92.82(2)∘, Z = 4 , R = 0.086 and RW = 0.085 .
Both complexes coordinated by a saddle shaped TAAB with an approximate S4 symmetry , and an anion on the axial site to form a distorted square pyramid stucture. The copper ion is generally located in the middle of the N4 plane . Average copper-nitrogen distances were found to be 1.937Å – 1.966Å for [Cu(TAAB)](CF3SO3)2 , 1.975Å – 2.039Å for [Cu(TAAB)](BF4)2 .
Based on electronic spectroscopic data, the reactions of [Cu(TRI)(CH3CN)](CF3SO3)、[Cu(TRI)(CH3CN)](BF4)、[Cu(CH3O-TRI)(CH3CN)](CF3SO3) with dioxygen suggest the formation (m-h2：h2-peroxo)dicopper (II) complexes. Similar reactions are also observed for complexes of 2-aminoacetophenone.

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