中文摘要
本研究以三牙基雙(2-啶甲基)胺(C12H13N3)及
2-(2-啶乙基)(2-啶甲基)胺(C13H15N3)為主要配子，合成下列二價銅及鎳的錯合物。包括六配位的錯合物：cis-fac-[Cu(dipica)2](ClO4)2、trans-fac-and sq-py-[Cu(dipica)2](ClO4)2、trans-fac-[Cu(pepica)2](ClO4)2、trans-fac-[Ni(dipica)2]Cl2.4H2O、trans-fac-[Ni(pepica)2]Cl2.2H2O；五配位的混合配基錯合物：[Cu(pepica)(bipy)](ClO4)2、 [Cu(pepica)(phen)](ClO4)2、[Cu(pepica)(neoc)](ClO4)2、 [Cu(pepica)(en)](ClO4)2、
[Cu(pepica)(pico)] (ClO4)2.(H2O)、[Cu(dipica)(neoc)](ClO4)2.(H2O)、[Cu(dipica)(bipy)](ClO4)2、 [Cu(dipica)(phen)](ClO4)2、 [Cu(dipica)Cl2]；四面配位的混合配基錯合物：[Cu(dipica)(H2O)](ClO4)2、 [Cu(dipica)(4ampy)](H2O)(ClO4)2、[Cu(dipica)(4phimH)](ClO4)2、[Cu(dipica)(4dmampy)](ClO4)2、[Cu(dipica)(nmim)](ClO4)2、 [Cu(dipica)(2mimH)](ClO4)2、[Cu(dipica)(4mimH)](ClO4)2、[Cu(pepica)(4dmampy)](ClO4)2、[Cu(pepica)(3mpy)](ClO4)2、 [Cu(pepica)(4mpy)](ClO4)2、
[Cu(pepica)(imH)](ClO4)2、 [Cu(pepica)(4mimH)](ClO4)2、 [Cu(pepica)(4ampy)](ClO4)2；雙核錯合物[Cu2(pepica)2Cl3]Cl；還有釩的含氧錯合物[VO2(bipy)](CF3SO3)和(C4H7N2)6V10O28.3H2O。
利用元素分析及紅外線光譜來確定錯合物的組成。紫外-可見光光譜、電子順磁共振光譜和X-光單晶繞射結構解析等方法，研究錯合物分子構造、軌域能層分佈及鍵結性質。錯合物的X-光單晶繞射結構解析，其資料如下：
(1) cis-fac-[Cu(dipica)2](ClO4)2，斜方晶系，空間群F2dd，晶格常數a = 8.832(5) A，b = 22.129(5) A，c = 28.428(8) A。晶胞值為4，精
算值R = 0.036，Rw = 0.023。
(2) trans-fac-and sq-py-[Cu(dipica)2](ClO4)2，單斜晶系，空間群P21/n，晶格常數a = 23.624(4) A，b = 9.369(4) A，c = 25.798(5) A，β = 95.60(2)°。晶胞值為4，精算值R = 0.059, Rw = 0.061。
(3) trans-fac-[Cu(pepica)2](ClO4)2，斜方晶系，空間群Pcab，晶格常數a = 12.028(4) A，b = 13.815(3) A，c = 17.701(5) A。晶胞值為4，精算值R = 0.050，Rw= 0.038。
(4) [Cu(pepica)(bipy)](ClO4)2，單斜晶系，空間群P21/c，晶格常數a = 12.98(2) A，b = 8.89(1) A，c = 22.61(3) A，β= 96.19(1)°。.晶胞值 為4，精算值R = 0.0732，Rw = 0.0859。
(5) [Cu(dipica)(phen)](ClO4)2，單斜晶系，空間群P21/n，晶格常數a = 13.627(4) A，b = 9.259 A (3)，c = 21.926(4) A，β= 106.71(2)°。
晶胞值為4，精算值R = 0.0530, Rw = 0.1525。
(6) [Cu(dipica)(nmim)](ClO4)2， 三斜晶系，空間群P1, 晶格常數 a = 8.4795(2)，b = 8.6999(2)， c = 16.4869(3) A；α= 78.821(1)，β= 82.938(1)，γ = 62.619(1)。晶胞值為2，精算值R = 0.0511， Rw = 0.059.
(7) [Cu(pepica)(4mpy)](ClO4)2， 三斜晶系，空間群 P-1，晶格常數 a = 8.690(3)， b = 8.808(3)， c = 18.017(6) A； α = 76.65(3)， β = 81.52(3)，γ = 63.16(3)°。晶胞值為2，精算值R = 0.080， Rw = 0.087。
(8) [Cu(pepica)(imH)](CH3CN)(ClO4)2，單斜晶系，空間群P21 /n ， 晶格常數a = 9.478(3)，b = 8.205(2)，c = 30.76(1) A； β = 93.11(3)°。
晶胞值為4，精算值R = 0.061，Rw =0.068。
(9) [Cu(dipica)Cl2]，單斜晶系，空間群P21/m，晶格常數a = 6.535(1) A，b = 13.375(3) A，c = 7.953(1) A，β = 103.38(1)°。晶胞值為4，精算值R = 0.028，Rw = 0.026。
(10) [Cu2(pepica)2Cl3]Cl，單斜晶系，空間群P21/n，晶格常數 a  8.960(2) A，b = 13.008(3) A，c = 24.861(7) A，β = 91.210(2)° 。晶胞值為4，精算值R = 0.029，Rw = 0.026。
(11) [Ni(dipica)2]Cl2. 4H2O，三斜晶系，空間群P-1，晶格常數a 
8.756(2) A，b = 9.449(3) A，c = 9.542(3) A，α= 74.10(3) ，β = 86.15(2) ，γ= 80.52(2)°。晶胞值為1，精算值R = 0.046，Rw =
0.055。
(12) [Ni(pepica)2]Cl2. 2H2O，單斜晶系，空間群P21/n，晶格常數a 
9.231(1) A，b = 9.016(1) A，c = 16.746(3) A，β = 104.01(1)° 。晶胞值為2，精算值R = 0.045，Rw = 0.037。
(13) [V(O)2(bipy)2](CF3SO3)，單斜晶系，空間群P21/n，晶格常數a 
15.433(2) A，b = 11.013(2) A，c = 27.423(2) A，β = 104.79(2)°。
晶胞值為4，精算值R = 0.0697, Rw = 0.0821。
(14) (C4H7N2)6V10O28.3H2O，三斜晶系，空間群P-1，晶格常數a =  9.596(2) A，b = 11.487(3) A，c = 12.318(2) A，α= 93.77(2)，β = 102.73(2)，γ= 106.73(2)°。晶胞值為1，精算值R = 0.032，Rw = 0.029。
比較錯合物的紫外-可見光光譜高斯交疊解析結果，對於固態及溶液態的cis-fac-[Cu(dipica)2](ClO4)2，其d軌域順序: dx2-y2 >> dz2 >
dxy > dyz > dxz；對於固態的trans-fac-[Cu(pepica)2](ClO4)2，dx2-y2 >> dxy > dz2 > dyz > dxz ；對於溶液態的trans-fac-[Cu(pepica)2](ClO4)2，dx2-y2 >> dxy > dyz ~ dz2 > dxz ; 對於溶液態的[Cu(pepica)(bipy)](ClO4)2、 [Cu(pepica)(phen)](ClO4)2、[Cu(pepica)(neoc)](ClO4)2、
、Cu(dipica)(neoc)](ClO4)2.(H2O)、[Cu(dipica)(en)](ClO4)2 、[Cu(pepica)(pico)](ClO4)2.(H2O)， dx2-y2 >> dz2 > dxy > dyz ~ dxz ；對於溶液態的[Cu(dipica)(bipy)](ClO4)2、[Cu(dipica)(phen)](ClO4)2，dx2-y2 >> dz2 > dxy > dyz > dxz ；對於溶液態的[Cu(dipica)(L)](ClO4)2及 [Cu(pepica)(L)](ClO4)2，dx2-y2 >> dxy dyz > dxz > dz2。

Abstract
The following Cu(II) complexes have been synthesized:
cis-fac-[Cu(dipica)2](ClO4)2, trans-fac-and sq-py-[Cu(dipica)2](ClO4)2, trans-fac-[Cu(pepica)2](ClO4)2, [Cu(pepica)(bipy)](ClO4)2, [Cu(pepica)(phen)](ClO4)2, [Cu(pepica)(neoc)](ClO4)2, [Cu(pepica)(en)](ClO4)2, [Cu(pepica)(pico)] (ClO4)2.(H2O), [Cu(dipica)(neoc)](ClO4)2.(H2O), [Cu(dipica)(bipy)](ClO4)2, [Cu(dipica)(phen)](ClO4)2, [Cu(dipica)(H2O)](ClO4)2,
[Cu(dipica)(4ampy)](H2O)(ClO4)2, [Cu(dipica)(4phimH)](ClO4)2, [Cu(dipica)(4dmampy)](ClO4)2, [Cu(dipica)(nmim)](ClO4)2, [Cu(dipica)(2mimH)](ClO4)2, [Cu(dipica)(4mimH)](ClO4)2, [Cu(pepica)(4dmampy)](ClO4)2, [Cu(pepica)(3mpy)](ClO4)2, [Cu(pepica)(4mpy)](ClO4)2, [Cu(pepica)(imH)](ClO4)2, [Cu(pepica)(4mimH)](ClO4)2, [Cu(pepica)(4ampy)](ClO4)2, [Cu(dipica)Cl2], [Cu2(pepica)2Cl3]Cl, trans-fac-[Ni(dipica)2]Cl2.5H2O, trans-fac-[Ni(pepica)2]Cl2.5H2O, [VO2(bipy)](CF3SO3), and (C4H7N2)6V10O28.3H2O.
These complexes have been characterized by elemental analyses, IR,UV-VIS and EPR spectroscopic measurements. X-ray crystal structures of the following complexes have been determined by using three-dimensional X-ray diffraction data.
(1) cis-[Cu(dipica)2](ClO4)2, orthorhombic, space group F2dd, a 
= 8.832(5) A, b = 22.129(5) A, c = 28.428(8) A, Z = 4, R = 0.036, Rw = 0.023.
(2) trans-fac-and sq-py-[Cu(dipica)2](ClO4)2, Monoclinic, space group P21/n, a= 23.624(4) A, b = 9.369(4) A, c = 25.798(5) A,
β = 95.60(2)°, Z = 4, R = 0.059, Rw = 0.061.
(3) trans-fac-[Cu(pepica)2](ClO4)2, Orthorhombic, space group Pcab ,a = 12.028(4) A, b = 13.815(3) A, c = 17.701(5) A, Z = 4, R = 0.050. Rw= 0.038.
(4) [Cu(pepica)(bipy)](ClO4)2, Monoclinic, space group P21/c, a 
= 12.98(2) A, b = 8.89(1) A, c = 22.61(3) A, β = 96.19(1)° , Z = 4, R = 0.0732, Rw = 0.0859.
(5) [Cu(dipica)(phen)](ClO4)2, Monoclinic, space group P21/ n, a = 13.627(4) A, b = 9.259 A (3), c = 21.926(4) A, β= 106.71(2)°, Z = 4, R = 0.0530, Rw = 0.1525.
(6) [Cu(dipica)(nmim)](ClO4)2, Triclinic, space group P-1, a 
8.4795(2), b = 8.6999(2), c = 16.4869(3) A; α = 78.821(1),
β = 82.938(1), γ= 62.619(1), Z = 2, R = 0.0511, Rw =0.059.
(7) [Cu(pepica)(4mpy)](ClO4)2, Triclinic, space group P-1, a 
8.690(3), b = 8.808(3), c = 18.017(6) A; α= 76.65(3),β = 81.52(3),γ = 63.16(3), Z = 2, Rf = 0.080，Rw =0.087.
(8) [Cu(pepica)(imH)](CH3CN)(ClO4)2, Monoclinic, space group P21/n a = 9.478(3), b = 8.205(2), c = 30.76(1) A; β = 93.11(3), Z = 4, R = 0.061，Rw =0.068
(9) [Cu(dipica)Cl2], Monoclinic, space group P21 / m, a =6.535(1) A, b = 13.375(3) A, c = 7.953(1) A, β = 103.38(1) , Z = 4, R = 0.028, Rw = 0.026.
(10) [Cu2(pepica)2Cl3]Cl, Monoclinic, space group P21/ n, a  8.960(2) A, b = 13.008(3) A, c = 24.861(7) A,β = 91.210(2) , Z = 4, R = 0.029, Rw = 0.026.
(11) [Ni(dipica)2]Cl2. 4H2O, Triclinic, space group P-1, a  8.756(2) A, b = 9.449(3) A, c = 9.542(3) A, α= 74.10(3) , β = 86.15(2) , γ= 80.52(2) , Z = 1, R = 0.046, Rw = 0.055.
(12) [Ni(pepica)2]Cl2. 2H2O, Monoclinic, space group P21 / n, a 
9.231(1) A, b = 9.016(1) A, c = 16.746(3) A, β = 104.01(1) , Z =2. R = 0.045, Rw = 0.037.
(13) [V(O)2(bipy)2](CF3SO3), Monoclinic, space group P21 / n, a 
15.433(2) A, b = 11.013(2) A, c = 27.423(2) A, β = 104.79(2) ,
Z = 4, R = 0.0697, Rw = 0.0821.
(1) (C4H7N2)6V10O28.3H2O, Triclinic, space group P-1, a =  9.596(2) A，b = 11.487(3) A, c = 12.318(2) A, α= 93.77, β =102.73(2), γ=106.73(2) , Z = 1, R = 0.032, Rw = 0.029.
Comparing the Gaussian component bands of the electronic spectra, the sequences of the d orbitals were assigned as dx2-y2 >> dz2 > dxy > dyz > dxz for solid and solution cis-[Cu(dipica)2](ClO4)2; dx2-y2 >> dxy > dz2 ~ dyz > dxz for solid trans-fac-[Cu(pepica)2](ClO4)2; dx2-y2 >> dxy > dyz ~ dz2 >  dxz for solution trans-fac-[Cu(pepica)2](ClO4)2; dx2-y2 >> dz2 > dxy > dyz ~ dxz for solution [Cu(pepica)(bipy)](ClO4)2, [Cu(pepica)(phen)](ClO4)2, [Cu(pepica)(neoc)](ClO4)2, [Cu(dipica)(neoc)](ClO4)2.(H2O), [Cu(dipica)(en)](ClO4)2 and [Cu(pepica)(pico)](ClO4)2.(H2O); dx2-y2 >> dz2 > dxy> dyz > dxz for solution [Cu(dipica)(bipy)](ClO4)2, and [Cu(dipica)(phen)](ClO4)2; dx2-y2 >> dxy > dyz > dxz > dz2 for solution [Cu(dipica)(L)](ClO4)2 and [Cu(pepica)(L)](ClO4)2.

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