為了解血青素金屬活性中心如何與氧氣進行可逆反應，本研究合成五個三牙基配子，N,N-雙(2-啶甲基)苯胺(Phdipica)、N,N-雙(2-啶甲基)-2-氫氧苯胺(HOPhdipica)、N,N-雙(2-啶甲基)三苯甲基胺(Ph3Cdipica)、N,N-雙(2-唑乙基)苯甲基胺(PhCH2dipyra)、N,N-雙(2-唑乙基)-2-氫氧苯胺(HOPhdipyra)，並以Phdipica、HOPhdipica的一價銅錯合物在室溫及低溫下與氧反應，Ph3Cdipica、PhCH2dipyra、HOPhdipyra的一價銅錯合物在室
溫下與氧反應，以電子吸收光譜判斷反應產物。
根據電子吸收光譜鑑定，Phdipica一價銅錯合物在室溫下可形成橋接過氧雙銅錯合物，而HOPhdipica一價銅錯合物在低溫(-30
℃)下亦可形成橋接過氧雙銅錯合物。
本研究亦以N,N-雙(2-啶甲基)苯胺(Phdipica)、N,N-雙(2-啶甲基)-2-氫氧苯胺(HOPhdipica)，為主要配子，合成了下列錯合物：[Cu(Phdipica)2](ClO4)2∙H2O、[Cu(Phdipica)(phen)](ClO4)2、[Cu(Phdipica)(bipy)](ClO4)2、[Cu(Phdipica)(acac)](ClO4)∙1.5H2O、[Cu(HOPhdipica)2](ClO4)2∙2H2O、[Cu2(OPhdipica)(phen)2](ClO4)3∙H2O、[Cu2(OPhdipica)(bipy)2](ClO4)3、[Cu(Ph3Cdipica)Br]、[Cu(dipica)Br2]，其中phen為1,10-二氮雜菲、bipy為2,2’-聯啶、acac為2,4-戊二酮。利用元素分析、紅外光光譜、紫外光-可見光吸收光譜、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。
目前己有X-光單晶結構解析的錯合物有：
1.[Cu(dipica)Br2]
屬於單斜晶系(Monoclinic)，空間群為P 21/m，晶格常數a = 6.774(1) Å；b = 13.422(2) Å；c = 8.269(2) Å； = 90； = 104.836(3) ； = 90，每單位晶格內含有2個分子(Z = 2)，精算值R = 0.0473，Rw = 0.1044。結
構為四角錐形體，dipica和一個溴構成基底面，另一個溴接於軸上。
2. [Cu2(dipica)2(OH)(H2O)](ClO4)3
屬於單斜晶系(Monoclinic)，空間群為C 2/c，晶格常數a = 24.571(8) Å；b = 8.562(3) Å；c = 15.341(5) Å； = 90.000(7) ，每單位晶格內含有4個分子(Z = 4)，精算值R = 0.1025，Rw = 0.2071。由dipica和一個OH-或H2O構成平面四方形。
綜合本研究得知，Phdipica、HOPhdipica為-acceptor性質的配子，在一系列錯合物中為面形(facial)形式與銅鍵結，而Ph3Cdipica亦可以採用面形的鍵結模式穩定一價銅，而形成[Cu(Ph3Cdipica)Br]。

In order to reveal the oxygen-carrying properties of hemocyanins , linear tridentate ligands including Phdipica (N,N-bis(2-pyridylmethyl)phenylamine), HOPhdipica (N,N-bis(2-pyridylmethyl)-2’-hydroxyphenylamine), Ph3Cdipica (N,N-bis(2-pyridylmethyl)triphenylmethylamine), PhCH2dipyra (N,N-bis(2-pyrazolylmethyl)benzylamine), and HOPhdipyra (N,N-bis(2-pyrazolylmethyl)-2’-hydroxyphenylamine) have been synthesized and charactered. The reactions of O2 with Cu(Ⅰ) complexes coordinated by these tridentate ligands at either room temp or low temp (-30℃) have been investigated. Based on the electronic spectral data [Cu(Phdipica)]+ at room temp and [Cu(HOPhdipica)]+ at low temp, are likely forming -2:2-peroxo complexes.
Nine mixed ligand copper (Ⅱ) complexes, [Cu(Phdipica)2](ClO4)2∙H2O、[Cu(Phdipica)(phen)](ClO4)2、[Cu(Phdipica)(bipy)](ClO4)2、[Cu(Phdipica)(acac)](ClO4)∙1.5H2O、[Cu(HOPhdipica)2](ClO4)2∙2H2O、[Cu2(OPhdipica)(phen)2](ClO4)3∙H2O、[Cu2(OPhdipica)(bipy)2](ClO4)3、[Cu(Ph3Cdipica)Br]、[Cu(dipica)Br2], where phen = 1,10-phenanthroline, bipy = 2.2’-bipyridine, acac = acetylacetonate, have been synthesized and characterized by elemental analyses, infrared, electronic absorption, and EPR spectroscopic
measurements.
By single-crystal X-ray diffraction method, the crystal and molecular structures of [Cu(dipica)Br2] and [Cu2(dipica)2(OH)(H2O)](ClO4)3 have been determined. The crystal data of these complexes are described below:
1. [Cu(dipica)Br2] crystallizes in the monoclinic space group P 21/m with a = 6.774(1) Å；b = 13.422(2) Å；c = 8.269(2) Å； = 90； = 104.836(3) ； = 90, Z = 2, R = 0.0473, Rw = 0.1044.
2. [Cu2(dipica)2(OH)(H2O)](ClO4)3 crystallizes in the monoclinic space group C2/c with a = 24.571(8) Å；b = 8.562(3) Å；c = 15.341(5) Å； = 90.000(7) , Z = 4, R = 0.1025, Rw = 0.2071.
In conclusion, both Phdipica and HOPhdipica tridentate ligands bind to copper d orbitals as -acceptors, and tend to retain a facial configuration. The stable copper(Ⅰ) complex, [Cu(Ph3Cdipica)Br], having a facial Ph3Cdipica was obtained by the reaction of Ph3Cdipica with CuBr2.

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