本研究係以三種醯胺基配子為主要研究的配子, 共合成四個系列二價銅錯
合物：(1) Cu(pmpa)(L)(X)(H2O)n 系列, 其中 pmpa 為 N-(2-
picolinyl)picolinamido,L 有咪唑(ImH), 1-甲基咪唑(NMIM), 4-甲基咪
唑(4MImH), 啶(py), 2-甲基啶(2Mpy), 3-甲基啶(3Mpy), 及 4-甲
基啶(4Mpy), 陰離子 X =ClO4-, BF4-, n = 0, 1 或 2.(2) Cu(pepa)(
L)(X)(H2O)n 系列, 其中 pepa 為 (N-(2-(2'-pyridine)aminoethyl)-
picolinamido, L 有咪唑(ImH), 1-甲基咪唑(NMIM), 2-甲基咪唑(2
MImH), 4-甲基咪唑(4MImH), 3-甲基啶(3Mpy), 及 4-甲基啶(4Mpy),
陰離子 X = ClO4-, BF4-, n = 0, 1 或 2.(3) Cu(depa)(L)(X)(H2O)n
系列, 其中 depa 為 N-(2-(N,N-dimethylaminoethyl) -picolinamido,
L 有 2-甲基咪唑(2MImH), 4-甲基咪唑(4MImH), X = ClO4-, n = 1.(4)
二價銅與三種醯胺基配子, 即 pepaH, pmpaH 及 depaH 及陰離子或 H2O
所形成之錯合物,, 分別有 Cu(pepa)(Cl)(H2O)2, Cu(pepa)(ClO4)(H2O),
Cu(pepa)(BF4)(H2O)3, Cu(pmpa)(Cl)(H2O), Cu(pmpa)(ClO4)(H2O),Cu(
pepa)(BF4)(H2O)4, 及Cu(depa)(ClO4) 等錯合物. 利用元素分析
及紅外光譜來確定銅錯合物的組成. 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, 研究各個銅錯合物分子構造, 軌域能
層分佈及鍵結性質. 每一系列均至少有一個供參考比較的 X -光單晶繞
射結構解析, 其資料如下：(1) [Cu(pmpa)(4MImH)(H2O)](H2O)(ClO4),
三斜晶系, 晶格常數 a =7.536(1) A, b = 10.269(1) A , c =
14.113(3) A, α = 75.09(1), β =76.48(1), γ = 88.45(1) °,晶胞
值為 2 ( Z = 2 ) 空間群 P1-, 精算值R =0.056, Rw = 0.062.(2)[Cu(
pmpa)(4Mpy)(H2O)](H2O)(ClO4) 三斜晶系, 晶格常數 a = 7.704(1)A, b
= 10.457(4) A , c = 13.917(2) A, α = 79.98(2), β = 75.81(1),
γ =87.33(2) °,晶胞值為 2( Z = 2 ), 空間群 P1-, 精算值 R =
0.051, Rw =0.55.(3) [Cu(pepa)(4MImH)(H2O)](H2O)(ClO4), 單斜晶系,
晶格常數 a = 7.337(2)A, b = 12.294(1) A , c = 22.293(2) A, β =
98.37(2)°, 晶胞值為 4 ( Z =4 ), 空間群 P21/c, 精算值 R =
0.070, Rw = 0.083.(4) [Cu(pepa)(3Mpy)(H2O)](ClO4), 單斜晶系, 晶
格常數 a = 7.493(3) A, b =12.591(2) A , c = 22.403(5) A, β =
98.38(2)°, 晶胞值為 4 ( Z = 4 ), 空間群 P21/n, 精算值 R =
0.046, Rw = 0.049.(5) [Cu(pepa)(4Mpy)(H2O)](ClO4), 單斜晶系, 晶
格常數 a = 7.322(1) A, b =24.426(2) A , c = 12.077(1) A, β =
96.38(2)°, 晶胞值為 4 ( Z = 4 ), 空間群 P21/c, 精算值 R =
0.043, Rw = 0.065.(6) [Cu(depa)(2MImH)(H2O)](ClO4), 單斜晶系, 晶
格常數 a = 19.779(3) A,b = 10.580(2) A , c = 18.919(4) A, β =
94.28(1)°, 晶胞值為 8 ( Z = 8 ),空間群 C2/c, 精算值 R = 0.045,
Rw = 0.049.(7) [Cu(pepa)(Cl)], 單斜晶系, 晶格常數 a = 9.176(2)
A, b = 11.993(2) A , c= 11.017(4) A, β = 93.41(2)°, 晶胞值為 4
( Z = 4 ), 空間群 P21/n, 精算值 R = 0.047, Rw = 0.069.(8) [Cu(
pepa)(H2O)2](ClO4), 單斜晶系, 晶格常數 a = 7.175(2) A, b
=22.337(9) A , c = 11.190(4) A, β = 91.80(2)°, 晶胞值為 4 ( Z
= 4 ), 空間群 P21/n, 精算值 R = 0.095, Rw = 0.104.(9) [Cu(pepa)(
H2O)2](BF4), 單斜晶系, 晶格常數 a = 7.163(1) A, b =21.944(4) A ,
c = 11.135(1) A, β = 91.99(1)°, 晶胞值為 4 ( Z = 4 ), 空間群
P21/n, 精算值 R = 0.083, Rw = 0.098. 比較系列(1)的錯合物
的紫外-可見光光譜高斯交疊解析結果, 本系列錯合物的 d 軌域順序, 依
結構的不同, 可分為兩種 : (a) 結構為拉長四角錐形體: dx2-y2 >> dz2
>dyz > dxy > dxz; (b) 扭曲平面方形 : dx2-y2 >> dyz >dxy > dxz
>dz2, 且三牙基 pmpa 為 π-供給基。比較系列(2)的錯合物的紫外-可見
光光譜高斯交疊解析結果, 此系列錯合物的 d 軌域順序: dx2-y2 >>dz2
>dyz > dxy > dxz; 且三牙基 pepa 為 π-供給基。

Four series of mixed ligand tridentate picolinamido
copper(II) complexeshave been prepared. They are :(1) Cu(pmpa)(
L)(X)(H2O)n type, where pmpa stands for N-(2-picolinyl)-
picolinamido, and L for imidazole(ImH), N-methylimidazole(NMIm),
4-methylimidazole(4MImH), pyridine(py), 2-methylpyridine(2Mpy),
3-methylpyridine(3Mpy), and 4-methylpyridine(4Mpy), and X for
ClO4-, or BF4-,and n = 0, 1 or 2.(2) Cu(pepa)(L)(X)(H2O)n type,
where pepa stands for (N-(2-(2'-pyridine)-aminoethyl)
picolinamido, and L for Imidazole(ImH), N-methylimidazole(NMIm),
2-methylimidazole(2MImH), 4-methylimidazole(4MImH),pyridine(py),
3-methylpyridine(3Mpy), and 4-methylpyridine(4Mpy) and X
forClO4-, or BF4-, n=0, 1 or 2. (3) Cu(depa)(L)(X)(H2O)n type,
where depa stands for N-(2-(N,N-dimethylaminoethyl)picolinamido
and L for 2-methylimidazole(2MImH), 4-methylpyridine(4Mpy), and
X for ClO4-, and n= 1. (4) Cu(L)(X)(H2O)n type, where L stands
for pepa, pmpa, depa, and X for Cl-ClO4-, or BF4-, and n= 0, 1,
2, 3, or 4. The mixed ligand copper(II) complexes have
been characterized byelemental analyses, and electronic,
vibrational, and EPR spectroscopicmeasurements. X-ray crystal
structures of the following complexes have beendetermined from
three-dimensional X-ray diffraction data.(1) [Cu(pmpa)(4MImH)(H2
O)](H2O)(ClO4), tirclinic, a = 7.536(1) A, b =10.269(1) A, c =
14.113(3) A,α = 75.09(1), β = 76.48(1), γ = 88.45(1) °, Z=
2, space group P1-, R = 0.056, Rw = 0.062.(2)[Cu(pmpa)(4Mpy)(H2
O)](H2O)(ClO4) tirclinic, a = 7.704(1) A, b = 10.457(4)A , c =
13.917(2) A, α = 79.98(2), β = 75.81(1), γ = 87.33(2) °, Z =
2, spacegroup P1-, R = 0.051, Rw = 0.55.(3) [Cu(pepa)(4MImH)(H2
O)](H2O)(ClO4), monoclinic, a = 7.337(2) A, b =12.294(1) A , c =
22.293(2) A, β = 98.37(2)°, Z = 4, space group P21/c, R
=0.070, Rw = 0.083.(4) [Cu(pepa)(3Mpy)(H2O)](ClO4), monoclinic,
a = 7.493(3) A, b = 12.591(2)A , c = 22.403(5) A, β =
98.38(2)°, Z = 4, space group P21/n, R = 0.046, Rw= 0.049.(5)
[Cu(pepa)(4Mpy)(H2O)](ClO4), monoclinic, a = 7.322(1) A, b =
24.426(2)A , c = 12.077(1) A, β = 96.38(2)°, Z = 4, space
group P21/c, R = 0.043, Rw =0.065.(6) [Cu(depa)(2MImH)(H2O)](
ClO4), monoclinic, a = 19.779(3) A, b =10.580(2) A , c =
18.919(4) A, β = 94.28(1)°, Z = 8, space group C2/c, R =0.045,
Rw = 0.049.(7) [Cu(pepa)(Cl)], monoclinic, a = 9.176(2) A, b =
11.993(2) A , c = 11.017(4)A, β = 93.41(2)°, Z = 4, space
group P21/n, R = 0.047, Rw = 0.069.(8) [Cu(pepa)(H2O)2](ClO4),
monoclinic, a = 7.175(2) A, b = 22.337(9) A , c =11.190(4) A, β
= 91.80(2)°, Z = 4, space group P21/n, R = 0.095, Rw =
0.104.(9) [Cu(pepa)(H2O)2](BF4), monoclinic, a = 7.163(1) A, b =
21.944(4) A , c =11.135(1) A, β = 91.99(1)°, Z = 4, space
group P21/n, R = 0.083, Rw =0.098. Comparing the
Gaussian component bands of electronic spectra, thesequences of
the d orbitals were assigned as dx2-y2 >> dz2 >dyz > dxy > dxz
forelongated square pyramidal complexes, and dx2-y2 >> dyz > dxy
> dxz >dz2 forsquare plannar complexes. It is obvious
that the energy of the dyz orbital of the mixed ligandcopper(II)
complexes was raised significantly, suggesting that the central
amidoN atom of the N-(2-picolinyl)picolinamido and the
(N-(2-(2'-pyridine)-aminoethyl)picolinamido are π-donor.
Four series of mixed ligand tridentate picolinamido