本研究以二羰基四氮環十四烷（dioxocyclamH2）為配子，搭配銅（Ⅱ）、鎳（Ⅱ）及鈷（Ⅲ）金屬，合成出〔Cu（dloxocyclam）（H2O）〕、[Cu(dioxocyclamH2)(py)(ClO4)](ClO4))、[Cu(dioxocyclamH2)(nmim)](ClO4)22H2O、[Ni(dioxocyclam)]6H2O及[Co(dioxocyclam)(CH3COO)L]nH2O等錯合物，其中L為單牙配子，分別為4-甲基咪口坐(4mimH)，4-苯基咪口坐(4phimH)及咪口坐(imH)。利用元術素分析、紅外線光譜、紫外光–可見光光譜、電子順磁共振光譜X–光結構解析等方法，完成錯合物結構的鑑定及鍵結性質的探採討。
本研究已完成之X–光單晶結構解析之金屬錯合物有:
(1)[Cu(dioxocyclam)(H2O)]
斜方晶系(ortnorhombic)，空間群(space group)：Pnma，晶格常數為：a＝10.7598(2)A，b＝9.4243(2)A，c＝12.5969(2)A，V＝1277.4(4)A3，每個單位晶格含有四個分子(Z＝4)，精算值R＝0.0345，Rw＝0.0355。
(2)Mi(dioxocyclam)]6H2O
單斜晶系(monoclinic)，空間群：P21/n，其晶格常數為：a＝7.3129(0)A，b＝25.1267(2)A，c＝9．4746(1)A，β＝92.207(2)°V＝1739.7(6)A3，每個單位晶格含有四個分子(Z=4)，精算值R＝0.0327，Rw＝0.0452。
(3)[Co(dioxocyclam)(CH3COO)(H20)]3H20
三斜晶系(triclinic)，空間群：P1，晶格常數為︰a＝7.565(3)A，b=9.457(l)A，c=12.778(5)A，α=100.32(2)°β=94.28(3)°，γ=90.24(2)°，V=896.7(5)A3，每個單位晶格含有二個分子(Z=2)，精算值R=0.037，Rw=0.039。
銅錯合物[Cu(dioxocyclam)(H2O)]由X-光結構解析得知為四方角錐，其電子順磁共振光譜為軸性光譜，g//與g⊥相當靠近，g⊥值有偏高之情形，電子光譜顯示其吸收於高能量區，鎳錯合物[Ni(dioxocyclam)6H2O為平面四方形結構，電子光譜之最大吸收峰於476nm，鈷錯合物[Co(dioxocyciam)(H2O)(CH3COO)]3H2O為八面體結構，電子光譜之最大吸收峰於613nm，[Co(dioxocyclam)(CH3COO)L]nH2O系列之電子光譜往短波位移。
銅系列錯合物經光譜鑑定及高斯交疊解析，軌域順序排列為dx2-y2＞＞dz2＞dxz～dyz＞dxy，鎳錯合物經高斯交疊解析，軌域順序排列為dxy＞＞dx2-y2＞dxz(ordyz)＞dyz(ordxz)＞dz2，在銅錯合物中，二羰基四氮環十四烷具有強烈的π-授予能力，但在鎳錯合物中，此配子只具強烈的σ-授予能力，而無明顯之π-授予能力。鈷錯合物系列經由電子光譜判定，其軸向分子的配位能力為：咪口坐類＞口比啶類＞H2O(or CH3COO-)＞cl-。

A series of mixed-ligand 1,4,8,ll-tetraazacyclotetradecane-5,7-dione (dioxocyclamH2) complexes of copper(Ⅱ), nickel(Ⅱ) and cobalt(Ⅲ) have been prepared and characterized by elemental analyses, electronic, vibrational, and epr spectroscopic measurements. The copper(Ⅱ) complexes include a square pyramidal [Cu(dioxocyclam)(H20)], and [Cu(dioxocyclamH2)(py)(CIO4)]CIO4 and [Cu(dioxocyclamH2(nmim)2] (CIO4)2．2H2O of tetragonal structure. Four cobalt(Ⅲ) complexes, [Co(dioxocyclam)(CH3COO)L]nH2O, where L represents H2O (n=3), imidazole (n=4), 4-methylimidazole (n=1.5), and 4-phenylimidazole (n=2), have been isolated, while only one nickel(Ⅱ) complex, [Ni(dioxocyclam)]6H2O, obtained.
X-ray crystal and molecular structures of the following complexes have been determined by three-dimensional X-ray diffraction data.
(1)[Cu(dioxocyclam)(H2O)] crystallizes in the orthorhombic, space group
Pnma with a=10.7595(2)A, b=9.4243(2)A, c=12.5969(2)A, V=
1277.4(4)A3, Z=4, R=0.0345, and Rw=0.0355.
(2)[Ni(dioxocyclam)]6H2O crystallizes in the monoclinic, space group
P21/n with a=7.3129(0)A, b=25.1267(2)A, c=9.4746(1)A, β=
92.207(2)°, V=1739.7(6)A3, Z=4, R=0.0327, and Rw=0.0452.
(3)[Co(dioxocyclam)(CH3COO)(H2O)]3H2O crystallizes in the triclinic, space group P1 with a=7.565(3)A, b=9.457(1)A, c=12.778(5)A,
a=100.32(2)°, β=94.28(3)°, γ=90.24(2)°, V=896.7(5)A3, Z=2, R=0.037, and Rw=0.039.
The structure of the copper(Ⅱ) complex, [Cu(dioxocyclam)(H2O)], is square pyramidal, and [Cu(dioxocyclamHi2)(py)(CIO4)](ClO4) and [Cu(dioxocyclamH2)(nmim)2](ClO4)2．2H2O are of tetragonal structure. The epr spectra of the copper(Ⅱ) complexes are axial type, and the electronic spectra appear in the high energy region. The structure of the nickel(Ⅱ) complex is square planar with λmax at a short wavelength of 476nm. The cobalt(Ⅲ) complexes are of octahedral structure. The λmax of [Co(dioxocyclam)(CH3COO)L]nH2O appear at 613nm for L=H2O, n=3, while shifted to shorter wavelengths for L=imidazoles.
The sequences of the d orbitals, deduced from the Gaussian analyses of the electronic spectra, have been assigned as dx2-y2＞＞dz2＞dxz～dyz＞dxy for the copper(Ⅱ) complexes, and dxy＞＞d2-y2＞dxz (or dyz)＞dyz (or dxz) ＞dz2 for the nickel(Ⅱ) complex. The dioxocyclam ligand is a strong π-donor in copper(Ⅱ) complexes, whereas, it is a strong σ-donor with no apparent π -donation capability in the Ni(Ⅱ) complex. The sequence of coordinate ability from electronic spectra for the cobalt complexes is imidazoles ＞pyridines ＞ H20 (or CH3COO-) ＞ Cl-.