總結 - 含L-組胺酸之掌性金屬錯合物之自組裝合成、結構多變性與性質研究

本論文使用具有掌性中心 (chiral center) 的分子^L-histidine，

合成出一系列金屬配位聚合物，研究此種具掌性的金屬配位聚合物的結構，並且針對其熱穩定性及水分子的吸脫附性質做探討。將合成出來的配位聚合物，依據搭配含氮配基不同，將其區分為：單體結構、

含 4,4’-bipyridine 的二維結構、含 5,5’-bipyrimidine 的二維及三維結構，包含三個系列六種結構相異的配位聚合物:

(四) [M(L-his)2]H2O [Zn(L-his)₂]H2O (1) [Ni(L-his)2]H2O (2)

(五) {[Cd(bipy)(L-his)(H₂O)]guest}_n {[Cd(bipy)(L-his)(H₂O)](ClO₄)}_n(3) {[Cd(bipy)(L-his)(H₂O)](NO₃)H2O}_n(4) (六) {[Cd(bpym)0.5(L-his)2(H2O)]guest}n

{[Cd(bpym)_0.5(L-his)₂(H₂O)](NO₃)C2H₅OH }_n(5) {[Cd(bpym)0.5(L-his)(H2O)](ClO4)H2O}n(6)

第一系列的合成中，利用使用不同的金屬，藉由金屬所偏好的配位數不同的關係，使得金屬和配基做鍵結時有不同的幾何結構，並且發現由於堆疊成三維超分子骨架的方式不同，使得兩個化合物的熱穩 定性相差甚大，在化合物 2 中，由於其單體結構堆疊成超分子骨架 時，單體和單體之間的作用力相當緊密，因此其熱穩定性相當高，這

樣的結果克服了過去認為單體結構熱穩定性不佳的問題。

第二系列則是使用剛性的含氮配基 4,4’-bipyridine，藉由改變陰 離子團，使化合物的孔洞大小改變。本系列之化合物 3、4 皆有水的 循環吸脫附性質，並且發現化合物 4 呈現明顯兩階段吸附和脫附的過 程，可以藉由溫度的調控將其分辨，並可得知吸附的過程為先進行化學吸附，再進行物理吸附。

第三系列中是改變含氮配基，藉由 5,5’-bipyrimidine 有較多位置可與金屬鍵結的特性，利用 5,5’-bipyrimidine 和金屬配位的位置不同，進而使金屬配位聚合物的維度由二維變成三維，發現當 bpym 以

cis form 和金屬鍵結，化合物會形成二維結構；當 bpym 以 trans form

和金屬鍵結時，則化合物為三維結構，另外，在此系列的化合物中，

L-histidine 的配位模式是相當少見的。

利用 L-histidine 與 4,4’-bipyridine 或 5,5’-bipyrimidine 合成化合物的這個方向，本篇論文中主要是利用硝酸根離子和過氯酸根離子團做合成，並比較其中的差異，所合成出來的化合物中，L-histidine 具有四種不同的配位模式，如表 5-1 所示，在過程之中，也有嘗試用其他的陰離子團做合成，但是所得到的結果沒有辦法由單晶知道其結構，有關陰離子交換的部分，也是未來實驗室可以繼續研究的地方，

並且在此論文中，是使用 L-form 的配基，如果可以利用相同的比例

續做 D-form 的合成，互相比較其性質，對實際應用上一定會有很大

compound 1 compound 2

O

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附錄

附錄一. [Zn(L-his)₂]H₂O(1) 的原子位置參數、熱運動參數、鍵長 (Å )、鍵角(°) 總表 Table 1.Crystal data and structure refinement for IC15559.

Identification code ic15559

Empirical formula C12H18N6ZnO5

Formula weight 391.37

Temperature 293(2) K

Wavelength 0.71073 Å

Crystal system tetragonal

Space group P43212

Density (calculated) 1.575 mg/m³

Absorption coefficient 1.464 mm^-1

F(000) 848

Theta range for data collection 3.82 to 27.86 °

Index ranges -8<=h<=9, -8<=k<=9, -33<=l<=39

Reflections collected 9152

Independent reflections 2005 [R(int) = 0.0255]

Completeness to theta = 27.86° 98.1 %

Refinement method Full-matrix least-squares on F² Data / restraints / parameters 2005 / 0 / 130

Goodness-of-fit on F² 0.929

Final R indices [I > 2(I)] R1 = 0.0304, wR2 = 0.1034

R indices (all data) R1 = 0.0353, wR2 = 0.1102

Absolute structure parameter -0.009(19)

Largest diff. peak and hole 0.288 and -0.244 e.Å^-3

Table 2.Atomic coordinates ( x 10⁴) and equivalent isotropic displacement parameters (Å²x 10³) for IC15559. U(eq) is defined as one third of the trace of the orthogonalized U^ij tensor.

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Table 3. Bond lengths [Å ] and angles [°] for IC15559.

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N(1)ZnN(1)#1 121.96(13)

N(1)ZnN(2) 95.71(9) N(1)#1ZnN(2) 116.51(8) N(1)ZnN(2)#1 116.51(8) N(1)#ZnN(2)#1 95.71(9) N(2)ZnN(2)#1 111.53(12) C(1)N(2)C(3) 107.0(2)

C(1)N(2)Zn 127.8(2)

C(3)N(2Zn 122.44(17)

C(2)C(3)N(2) 107.0(2) C(2)C(3)C(4) 129.3(3) N(2)C(3)C(4) 123.7(2) N(1)C(5)C(6) 110.5(2) N(1C(5)C(4) 109.7(2) C(6)C(5)C(4) 110.59(19) C(3)C(4)C(5) 113.6(2) C(3)C(2)N(3) 107.8(3) N(2)C(1)N(3) 110.0(3) C(1N(3)C(2) 108.2(2)

C(5)N(1)Zn 113.75(14)

O(1)C(6)O(2) 124.1(3) O(1)C(6)C(5) 118.4(2) O(2)C(6)C(5) 117.4(2)

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Symmetry transformations used to generate equivalent atoms : #1 y, x, -z+1

附錄二. [Ni(L-his)₂]H₂O(2) 的原子位置參數、熱運動參數、鍵長 (Å )、鍵角(°) 總表 Table 1.Crystal data and structure refinement for ic15523.

Identification code ic15523

Empirical formula C12H18N6NiO5

Formula weight 384.71

Temperature 295(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group C2

Density (calculated) 1.666 mg/m3

Absorption coefficient 1.302 mm-1

F(000) 800

Crystal size 0.38 x 0.30 x 0.06 mm3

Theta range for data collection 1.38 to 27.50 °

Index ranges -36<=h<=38, -10<=k<=10, -8<=l<=8

Reflections collected 7498

Independent reflections 3453 [R(int) = 0.0328]

Completeness to theta = 27.50° 99.8 %

Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9259 and 0.6374

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3453 / 1 / 217

Goodness-of-fit on F2 1.039

Final R indices [I > 2(I)] R1 = 0.0346, wR2 = 0.0751

R indices (all data) R1 = 0.0388, wR2 = 0.0874

Absolute structure parameter 0.008(15)

Largest diff. peak and hole 0.427 and -0.230 e.Å -3

Table 2.Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å 2x 103) for ic15523. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

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x y z U(eq)

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Ni 3677(1) 9333(1) 2681(1) 23(1)

Table 3.Bond lengths [Å ] and angles [°] for ic15523.

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NiN(6) 2.073(3)

N(6NiN(3) 101.06(11)

N(6NiN(4) 88.77(12)

N(3NiN(4) 93.08(11)

N(6NiN(1) 97.25(1)

N(3NiN(1) 89.85(1)

N(4NiN(1) 172.69(1)

N(6Ni-O(3) 79.37(1)

N(4NiO(3) 87.52(1)

N(1NiO(3) 89.50(1)

N(6NiO(1) 177.23(1)

N(3NiO(1) 78.17(1)

N(4NiO(1) 88.62(1)

N(1NiO(1) 85.43(1)

O(3NiO(1) 101.44(9)

C(6O(1)Ni 111.0(2)

C(12O(3)Ni 112.5(2)

C(1N(1)C(3) 105.4(3)

C(11N(6)Ni 105.5(2)

N(1C(1)N(2) 111.9(3) C(8C(9C(10) 129.2(4) N(4C(9C(10) 121.9(3) C(9C(10C(11) 115.9(3) N(6C(11C(10) 109.7(3)

C(10C(11C(12) 112.8(3) O(4C(12O(3) 124.4(3) O(4C(12C(11) 118.0(3) O(3C(12C(11) 117.6(3)

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Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å 2x 10 3) for IC15559.

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x y z U(eq)

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H(5A) -5174 -11523 4973 51

H(4A) -2893 -10570 5411 63

H(4B) -2807 -9364 4993 63

H(2A) -2011 -8439 6067 82

H(1B) -4990 -4322 5776 69

H(3A) -2949 -5530 6287 94

H(1) -7110(50) -9530(40) 4714(11) 57(9)

H(3D) -2710(30) -10580(30) 4191(8) 38(5)

H(3C) -3760(70) -8650(60) 4009(19) 42(9)

H(1A) -5260(50) -9210(40) 4540(14) 69(10)

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附錄三.{[Cd(4,4’-bipy)(L-his)(H2O)](ClO4)}n (3) 的原子位置參數、熱運動參數、鍵長 (Å )、鍵角(°) 總表

Table 1.Crystal data and structure refinement for ic15706.

Identification code ic15706

Empirical formula C16H18CdClN5O7

Formula weight 539.99

Temperature 295(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P21

Density (calculated) 1.803 mg/m3

Absorption coefficient 1.282 mm-1

F(000) 540

Crystal size 0.45 x 0.45 x 0.10 mm3

Theta range for data collection 2.08 to 27.56°

Index ranges -13<=h<=13, -11<=k<=8, -15<=l<=15

Reflections collected 8044

Independent reflections 3876 [R(int) = 0.0267]

Completeness to theta = 27.56° 99.5 %

Absorption correction None

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3876 / 1 / 283

Goodness-of-fit on F2 1.028

Final R indices [I > 2(I)] R1 = 0.0279, wR2 = 0.0675

R indices (all data) R1 = 0.0294, wR2 = 0.0685

Absolute structure parameter 0.00(3)

Largest diff. peak and hole 0.477 and -0.811 e.Å -3

Table 2.Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å 2x 103) for ic15706. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

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Table 3.Bond lengths [Å ] and angles [°] for ic15706.

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CdN(5)#1 2.328(3)

C(15)C(16) 1.527(5)

N(5)#1CdN(1) 94.57(15) N(5)#1CdN(2)#2 88.89(14) N(1)CdN(2)#2 175.8(3) N(5)#1CdO(2) 148.34(15)

N(1)CdO(2) 91.67(9)

N(2)#2CdO(2) 86.61(8) N(5)#1CdO(3) 80.84(13)

N(1)CdO(3) 87.39(19)

N(2)#2CdO(3) 90.80(18)

O(2)CdO(3) 130.50(15)

N(5)#1CdO(1)#1 70.20(11)

N(1)CdO(1)#1 95.8(2)

N(2)#2CdO(1)#1 87.6(2) O(2)CdO(1)#1 78.31(13) O(3)CdO(1)#1 151.01(12) N(5)#1CdO(1) 157.53(11)

N(1CdO(1) 90.25(17)

N(2)#2CdO(1) 85.65(17)

O(2CdO(1) 53.04(13)

O(3CdO(1) 77.47(12)

O(1)#1CdO(1) 131.15(3)

O(7ClO(6) 114.6(4)

C(16O(1)Cd#3 117.9(2)

C(16O(1)Cd 89.0(2)

Cd#3O(1Cd 152.73(12)

C(16O(2Cd 96.1(2)

C(5N(1C(1) 116.8(3)

C(5N(1Cd 119.2(2)

C(1N(1Cd 123.9(2)

C(6N(2C(10) 116.8(3) C(6N(2Cd#4 119.7(3)

C(11N(3C(12) 107.9(5) C(11N(4C(13) 105.4(5) C(15N(5Cd#3 114.7(2) N(1C(1C(2) 123.0(3) C(10C(9C(8) 119.3(4) N(2C(10C(9) 123.2(4) N(4C(11N(3) 111.3(5) C(13C(12N(3) 105.8(6) C(12C(13N(4) 109.5(4) C(12C(13C(14) 128.5(4) N(4)C(13C(14) 121.9(4) C(13C(14C(15) 113.9(3) N(5C(15C(16) 110.6(3) N(5C(15C(14) 112.1(3) C(16C(15C(14) 112.5(3) O(2C(16O(1) 121.5(3) O(2C(16C(15) 119.1(3) O(1)C(16)C(15) 119.1(3)

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Symmetry transformations used to generate equivalent atoms：

#1 -x+2, y-1/2, -z+2 #2 x, y, z+1 #3 -x+2, y+1/2, -z+2 #4 x, y, z-1

Table 4.Anisotropic displacement parameters (Å 2x 103) for ic15706. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] __________________________________________________________________________

U11 U22 U33 U23 U13 U12

Table 5.Hydrogen coordinates ( x 10⁴) and isotropic displacement parameters (Å²x 10³) for ic15706.

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x y z U(eq)

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H(3B) 12220(50) 8170(70) 10570(40) 50(14)

附錄四.{[Cd(4,4’-bipy)(L-his)(H₂O)](NO₃)H₂O}_n(4) 的原子位置參數、熱運動參數、鍵長 (Å )、鍵角(°) 總表

Table 1.Crystal data and structure refinement for ic15486.

Identification code ic15486

Empirical formula C16H20CdN6O7

Formula weight 519.77

Temperature 150(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P21

Density (calculated) 1.732 mg/m3

Absorption coefficient 1.148 mm-1

F(000) 522

Crystal size 0.40 x 0.14 x 0.02 mm3

Theta range for data collection 1.74 to 27.50°

Index ranges -12<=h<=12, -10<=k<=11, -15<=l<=15

Reflections collected 9578

Independent reflections 4477 [R(int) = 0.0426]

Completeness to theta = 27.50° 100.0 %

Absorption correction None

Max. and min. transmission 0.9774 and 0.6567

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4477 / 1 / 275

Goodness-of-fit on F2 1.044

Final R indices [I > 2(I)] R1 = 0.0373, wR2 = 0.0731

R indices (all data) R1 = 0.0416, wR2 = 0.0748

Absolute structure parameter 0.03(3)

Largest diff. peak and hole 0.972 and -1.062 e.Å -3

Table 2.Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å 2x 103) for ic15486. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

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x y z U(eq)

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Cd 3841(1) 7772(1) 9765(1) 15(1)

Table 3.Bond lengths [Å ] and angles [°] for ic15486.

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CdO(3) 2.290(3)

O(3CdN(2) 93.5(2) O(2)#1CdN(2) 93.04(10)

O(3CdO(1) 158.90(11)

O(2)#1CdO(1) 74.9(2)

N(2)CdO(1) 92.2(2)

O(3CdN(1) 85.1(2)

O(2)#1CdN(1) 88.43(9)

N(2CdN(1) 178.4(2)

O(1CdN(1) 88.8(2)

O(3CdN(5) 88.40(13)

O(2)#1CdN(5) 146.6(2)

N(2CdN(5) 86.10(16)

O(1CdN(5) 71.74(11)

N(1CdN(5) 93.06(16)

C(16O(1Cd 118.9(3)

C(16O(2Cd#2 101.3(4) C(5N(1C(1) 116.6(3)

C(5N(1Cd 124.2(3)

C(1N(1Cd 119.2(3)

C(6N(2C(10) 116.9(3)

C(6N(2Cd 122.4(4)

C(10N(2Cd 120.6(4)

C(11N(3C(12) 107.3(5) C(11N(4C(13) 105.8(4)

C(15N(5Cd 115.1(3)

N(1C(1C(2) 123.7(4) C(1C(2C(3) 119.7(4) C(4C(3C(2) 116.7(4) C(4)C(3C(8)#3 122.0(4) C(2C(3C(8)#3 121.3(4) C(3C(4C(5) 119.6(4) N(1C(5C(4) 123.8(4) N(2C(6C(7) 123.8(4) C(6C(7C(8) 118.9(4) C(9C(8C(7) 117.3(4) C(9C(8C(3)#4 121.7(5) C(7C(8C(3)#4 121.0(5) C(8C(9C(10) 119.3(4)

N(4)C(11)N(3) 111.8(5) C(13)C(12)N(3) 106.9(5) C(12)C(13)N(4) 108.2(5) C(12)C(13)C(14) 131.2(5) N(4)C(13)C(14) 120.5(4) C(13)C(14)C(15) 112.3(4) N(5)C(15)C(14) 112.2(4) N(5)C(15)C(16) 111.2(4) C(14)C(15)C(16) 111.8(4) O(4)N(6)O(5) 121.2(6) O(4)N(6)O(6) 121.1(5) O(5)N(6)O(6) 117.6(5) O(1)C(16)O(2) 121.3(4) O(1)C(16)C(15) 121.3(4) O(2)C(16)C(15) 117.3(4)

________________________________________________________________ _____

Symmetry transformations used to generate equivalent atoms：

#1 -x+1, y-1/2, -z+2 #2 -x+1, y+1/2, -z+2 #3 x, y, z+1 #4 x, y, z-1

Table 4.Anisotropic displacement parameters (Å 2x 103) for ic15486. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] __________________________________________________________________________

U11 U22 U33 U23 U13 U12

__________________________________________________________________________

Cd 18(1) 13(1) 14(1) 0(1) 1(1) 0(1)

Table 5.Hydrogen coordinates ( x 10⁴) and isotropic displacement parameters (Å²x 10³) for ic15486.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

H(3A) 1607 5614 9396 34

附錄五.{[Cd(5,5’-bpym)_0.5(L-his)(H₂O)](NO₃)C₂H₅OH}_n(5) 的原子位置參數、熱運動參數、鍵長 (Å )、鍵角(°) 總表

Table 1.Crystal data and structure refinement for ic16087.

Identification code ic16087

Empirical formula C12H19CdN6O7

Formula weight 47104

Temperature 150(2) K

Wavelength 0.71073 Å

Crystal system Orthorhombic

Space group P21212

Density (calculated) 1.677 mg/m3

Absorption coefficient 1.431 mm-1

F(000) 772

Crystal size 0.42 x 0.15 x 0.15 mm3

Theta range for data collection 2.00 to 27.53°

Index ranges -11<=h<=11, -26<=k<=26, -11<=l<=11

Reflections collected 15554

Independent reflections 3583 [R(int) = 0.0429]

Completeness to theta = 27.53° 100.0 %

Absorption correction None

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3583 / 0 / 248

Goodness-of-fit on F2 1.108

Final R indices [I > 2(I)] R1 = 0.0354, wR2 = 0.0915

R indices (all data) R1 = 0.0365, wR2 = 0.0921

Absolute structure parameter 1.01(4)

Largest diff. peak and hole 0.556 and -1.075 e.Å -3

Table 2.Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å 2x 103) for ic16087. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

__________________________________________________________________________

x y z U(eq)

__________________________________________________________________________

Cd(1) 6353(1) 2079(1) 742(1) 17(1)

Table 3.Bond lengths [Å ] and angles [°] for ic16087.

_____________________________________________________

Cd(1)O(3) 2.267(4)

O(3)Cd(1)N(1) 101.82(19) O(3)Cd(1)O(1)#1 124.10(16) N(1)Cd(1)O(1)#1 98.09(14) O(3)Cd(1)N(3) 86.83(16) N(1)Cd(1)N(3) 81.57(17) O(1)#1Cd(1)N(3) 147.93(16) O(3)Cd(1)N(4) 86.95(18) N(1)Cd(1)N(4) 169.79(15) O(1)#1Cd(1)N(4) 80.94(13) N(3)Cd(1)N(4) 93.83(18) O(3)Cd(1)O(2) 154.58(14) N(1)Cd(1)O(2) 85.20(15) O(1)#1Cd(1)O(2) 78.11(12) N(3)Cd(1)O(2) 69.89(14) N(4)Cd(1)O(2) 84.65(14) O(3)Cd(1)O(2)#1 76.36(14) N(1)Cd(1)O(2)#1 89.94(13) O(1)#1Cd(1)O(2)#1 51.89(12) N(3)Cd(1)O(2)#1 159.24(15) N(4)Cd(1)O(2)#1 97.29(14) O(2)Cd(1)O(2)#1 128.50(5) C(7)N(4)C(8) 116.3(4) C(7)N(4)Cd(1) 118.1(3) C(8)N(4)Cd(1) 125.2(4) N(5)C(10)C(9) 122.7(5) C(7)N(5)C(10) 115.2(4) C(8)C(9)C(10) 117.2(5) C(8)C(9)C(9)#2 122.5(4) C(10)C(9)C(9)#2 120.2(4) N(1)C(1)N(2) 110.2(5) C(1)N(2)C(2) 108.1(5) N(5)C(7)N(4) 127.4(5) N(4)C(8)C(9) 121.2(5) O(4)N(6)O(5) 120.4(3) O(4)N(6)O(5)#3 120.4(3) O(5)N(6)O(5)#3 119.2(6) C(1)N(1)C(3) 105.9(5) C(1)N(1)Cd(1) 125.6(4)

C(5)N(3)Cd(1) 107.7(3) C(3)C(2N(2) 107.0(5) O(6)N(7O(6)#4 128.2(7) O(6)N(7O(7)#4 108.1(5) O(6)#4N(7)O(7)#4 110.3(4) O(6)N(7)O(7) 110.3(4) O(6)#4N(7)O(7) 108.1(5) O(7)#4N(7)O(7) 82.3(8) N(7)O(7)C(11) 144.4(7) C(12)C(11)O(7) 159.6(9) C(12)#5C(12)C(11) 118.4(8) C(2)C(3)N(1) 108.9(5) C(2)C(3)C(4) 126.8(5) N(1)C(3)C(4) 124.3(4) C(6)O(1)Cd(1)#6 98.9(3) C(3)C(4)C(5) 117.7(4) C(6)O(2)Cd(1) 112.2(3) C(6)O(2)Cd(1)#6 85.0(3) Cd(1)O(2)Cd(1)#6 142.80(16)

_____________________________________________________________

Symmetry transformations used to generate equivalent atoms：

#1 x-1/2, -y+1/2, -z #2 -x+1, -y, z #3 -x+1, -y+1, z

#4 -x+1, -y+2, z #5 -x+2, -y+2, z #6 x+1/2, -y+1/2, -z

Table 4.Anisotropic displacement parameters (Å 2x 103) for ic16087. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] __________________________________________________________________________

U11 U22 U33 U23 U13 U12

Table 5.Hydrogen coordinates ( x 10⁴) and isotropic displacement parameters (Å²x 10³) for ic16087.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

H(10) 6471 188 -4446 27

H(1) 5567 3564 2281 35

H(2A) 6945 4085 4293 42

H(7) 7531 1855 -2549 28

H(8) 4767 639 -406 31

H(2) 9035 3370 5245 39

H(11A) 8401 10282 1529 83

H(11B) 8079 9532 1667 83

H(4A) 8760 1864 4729 33

H(4B) 10264 2249 4145 33

H(5A) 10063 1280 2826 25

H(3D) 3480(80) 1790(30) 1630(70) 16(16)

H(3A) 7970(90) 1080(40) 1700(90) 50(20)

H(3C) 4880(180) 1840(70) 2140(160) 150(60)

H(3B) 7210(110) 1440(40) 3080(100) 70(30)

________________________________________________________________________________

附錄六. {[Cd(5,5’-bpym)_0.5(L-his)(H₂O)](ClO₄)H₂O}_n(6) 的原子位置參數、熱運動參數、鍵長 (Å )、鍵角(°) 總表

Table 1.Crystal data and structure refinement for ic15910.

Identification code ic15910

Empirical formula C10H15CdClN5O8

Formula weight 481.02

Temperature 150(2) K

Wavelength 0.71073 Å

Crystal system Tetragonal

Space group P43212

Density (calculated) 1.940 mg/m3

Absorption coefficient 1.534 mm-1

F(000) 1950

Crystal size 0.25 x 0.25 x 0.15 mm3

Theta range for data collection 1.79 to 27.50°.

Index ranges -9<=h<=11, -11<=k<=11, -58<=l<=59

Reflections collected 12596

Independent reflections 3710 [R(int) = 0.0709]

Completeness to theta = 27.50° 99.3 %

Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.791 and 0.606

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3710 / 8 / 218

Goodness-of-fit on F2 1.062

Final R indices [I > 2(I)] R1 = 0.0581, wR2 = 0.1520

R indices (all data) R1 = 0.0776, wR2 = 0.1665

Absolute structure parameter -0.02(8)

Extinction coefficient 0.0120(12)

Largest diff. peak and hole 1.320 and -0.968 e.Å -3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å 2 x 103) for ic15910. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

__________________________________________________________________________

x y z U(eq)

__________________________________________________________________________

Cd(1) 13240(1) 11117(1) 8971(1) 38(1)

__________________________________________________________________________

Table 3. Bond lengths [Å ] and angles [°] for ic15910.

_____________________________________________________

Cd(1)N(1)#1 2.263(7)

O(5'O(5')#3 1.09(4) O(5')Cl(1')#3 2.14(2)

N(1)#1Cd(1)O(3) 99.9(2) N(1)#1Cd(1)O(1) 97.9(2) O(3)Cd(1)O(1) 119.8(2) N(1)#1Cd(1)N(3)#1 84.1(3) O(3)Cd(1)N(3)#1 93.3(2) O(1)Cd(1)N(3)#1 145.6(2) N(1)#1Cd(1)N(4) 171.4(3) O(3)Cd(1)N(4) 86.8(2) O(1)Cd(1)N(4) 83.2(2) N(3)#1Cd(1)N(4) 90.2(3) N(1)#1Cd(1)O(2)#1 83.5(2) O(3)Cd(1)O(2)#1 161.43(19) O(1)Cd(1)O(2)#1 77.3(2) N(3)#1Cd(1)O(2)#1 68.8(2) N(4)Cd(1)O(2)#1 88.4(2) C(6)O(1)Cd(1) 101.7(5) C(6)O(2)Cd(1)#2 110.1(5) C(1)N(1)C(3) 105.7(7) C(1)N(1)Cd(1)#2 124.8(6) C(3) N(1)Cd(1)#2 127.9(5) C(1)N(2)C(2) 106.2(8) C(5)N(3)Cd(1)#2 108.6(4) C(8)N(4)C(7) 115.1(7) C(8)N(4Cd(1) 124.4(6) C(7)N(4)Cd(1) 118.5(5) C(7)N(5)C(10) 117.3(9) N(1)C(1)N(2) 111.5(9)

O(2)C(6)C(5) 122.5(7) O(1)C(6)C(5) 116.0(7) N(5)C(7)N(4) 127.9(7) N(4)C(8)C(9) 122.9(8) C(8)C(9)C(10) 116.9(7) C(8)C(9)C(9)#3 121.4(10) C(10)C(9)C(9)#3 121.5(10) N(5)C(10)C(9) 119.8(9) O(4)Cl(1)O(6) 110.2(18) O(4)Cl(1)O(5) 117(2) O(6)Cl(1)O(5) 104.5(16) O(4)Cl(1)O(7) 118.0(17) O(6)Cl(1)O(7) 107.1(14) O(5)Cl(1)O(7) 98.7(13) O(5)#4O(5)Cl(1) 137(3) O(5')Cl(1')O(7') 114.8(15) O(5')Cl(1')O(6') 95.6(18) O(7')Cl(1')O(6') 96.5(15) O(5')Cl(1')O(4') 112.5(19) O(7')Cl(1')O(4') 111.4(18) O(6')Cl(1')O(4') 124.7(18) O(5')Cl(1')O(5')#3 26.8(15) O(7')Cl(1')O(5')#3 88.0(14) O(6')Cl(1')O(5')#3 99.3(16) O(4')Cl(1')O(5')#3 127.2(16) O(5')#3O(5')Cl(1') 118(3) O(5')#3O(5')Cl(1')#3 35.5(15) Cl(1')O(5')Cl(1')#3 114.0(17)

_____________________________________________________

Symmetry transformations used to generate equivalent atoms：

#1 -x+5/2, y+1/2, -z+7/4 #2 -x+5/2, y-1/2, -z+7/4

#3 y, x, -z+2 #4 y-1, x+1, -z+2

Table 4. Anisotropic displacement parameters (Å 2x 103) for ic15910. The anisotropic

Table 5.Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å 2x 10 3) for ic15910.

__________________________________________________________________________

x y z U(eq)

__________________________________________________________________________

H(2A) 8568 6808 9492 85

H(3A) 10797 7901 8044 60

H(3B) 9346 7127 8157 60

H(1) 10514 5370 9214 68

H(2) 7293 8785 9169 89

H(4A) 7594 8330 8465 66

H(4B) 8027 9904 8636 66

H(5) 9495 9950 8220 53

H(7) 9620 11779 9084 71

H(8) 12535 10148 9676 59

H(10) 8152 11643 9904 80

__________________________________________________________________________

附錄七.化合物1之紅外線光譜圖

附錄八.化合物2之紅外線光譜圖

4000 3000 2000 1000

Wavenumber (cm-1)

102110741120127513231337

141714451480

15801615

No cm-1 %T Intensity 1 562.00 65.931 M 2 632.00 67.494 M 3 717.00 69.689 M 4 776.00 75.321 W 5 821.00 72.272 W 6 892.00 68.509 M

No cm-1 %T Intensity 7 1021.00 63.524 M 8 1074.00 54.375 M 9 1120.00 58.174 M 10 1195.00 62.659 M 11 1275.00 61.930 M 12 1323.00 59.021 M

No cm-1 %T Intensity 13 1337.00 55.617 M 14 1417.00 54.960 M 15 1445.00 59.326 M 16 1480.00 66.448 M 17 1506.00 68.196 M 18 1580.00 35.507 VS

No cm-1 %T Intensity 19 1615.00 41.320 S 20 2662.00 69.496 M 21 2907.00 62.106 M 22 3106.00 48.112 S 23 3317.00 58.025 M 24 3479.00 51.729 S

4000 3000 2000 1000

Wavenumber (cm-1)

906101510761109116012711316

140014351482

1588

2651

2941

3179

3308

No cm-1 %R Intensity 1 559.00 57.636 M 2 627.00 47.371 M 3 654.00 53.168 M 4 713.00 55.732 M 5 818.00 49.474 M

No cm-1 %R Intensity 6 906.00 58.555 M 7 1015.00 57.412 M 8 1076.00 32.292 S 9 1109.00 52.007 M 10 1160.00 56.129 M

No cm-1 %R Intensity 11 1271.00 56.389 M 12 1316.00 49.678 M 13 1400.00 34.343 S 14 1435.00 39.873 S 15 1482.00 50.483 M

No cm-1 %R Intensity 16 1588.00 21.372 VS 17 2651.00 58.295 M 18 2941.00 46.532 M 19 3179.00 36.404 S 20 3308.00 43.845 S

附錄九.化合物3之紅外線光譜圖

附錄十. 化合物4之紅外線光譜圖

4000 3000 2000 1000

Wavenumber (cm-1)

%Transmittance 428491538564631727776806

9269681008

1076115012211252

138514151464

16031635

1942

3056

3396

No cm-1 %T Intensity 1 428.00 67.418 W 2 491.00 54.771 M 3 538.00 60.786 W 4 564.00 60.863 W 5 631.00 36.489 S 6 727.00 58.511 M

No cm-1 %T Intensity 7 776.00 59.789 M 8 806.00 28.463 S 9 926.00 68.344 W 10 968.00 68.776 W 11 1008.00 59.462 M 12 1044.00 64.901 W

No cm-1 %T Intensity 13 1076.00 57.029 M 14 1150.00 64.839 W 15 1221.00 45.206 M 16 1252.00 54.530 M 17 1385.00 20.109 VS 18 1415.00 22.063 VS

No cm-1 %T Intensity 19 1464.00 33.841 S 20 1603.00 23.988 VS 21 1635.00 33.296 S 22 1942.00 65.825 W 23 3056.00 32.780 S 24 3396.00 28.154 S

4000 3000 2000 1000

Wavenumber (cm-1)

No cm-1 %T Intensity 1 491.00 24.763 S 2 630.00 11.793 VS 3 806.00 12.864 VS

No cm-1 %T Intensity 4 1007.00 26.515 M 5 1090.00 10.242 VS 6 1115.00 11.966 VS

No cm-1 %T Intensity 7 1139.00 12.510 VS 8 1221.00 23.708 S 9 1414.00 15.371 S

No cm-1 %T Intensity 10 1490.00 26.234 M 11 1603.00 10.716 VS 12 3292.00 13.085 VS

附錄十一.化合物5之紅外線光譜圖

附錄十二.化合物6之紅外線光譜圖

4000 3000 2000 1000

Wavenumber (cm-1)

No cm-1 %T Intensity 1 649.00 26.100 S 2 717.00 22.051 S 3 825.00 31.605 M

No cm-1 %T Intensity 4 908.00 42.307 W 5 1006.00 38.206 M 6 1055.00 36.621 M

No cm-1 %T Intensity 7 1189.00 32.902 M 8 1270.00 39.329 M 9 1385.00 12.661 VS

No cm-1 %T Intensity 10 1410.00 11.257 VS 11 1582.00 12.910 VS 12 3382.00 17.389 S

4000 3000 2000 1000

Wavenumber (cm-1)

No cm-1 %T Intensity 1 474.00 25.738 M 2 565.00 16.182 S 3 627.00 9.477 VS 4 720.00 13.427 S

No cm-1 %T Intensity 5 824.00 21.791 S 6 895.00 21.782 S 7 932.00 30.734 M 8 1008.00 17.919 S

No cm-1 %T Intensity 9 1107.00 6.774 VS 10 1272.00 33.460 M 11 1321.00 14.338 S 12 1408.00 10.157 VS

No cm-1 %T Intensity 13 1447.00 15.625 S 14 1557.00 6.901 VS 15 2920.00 32.133 M 16 3334.00 12.494 S

附錄十三.L-histidine之紅外線光譜圖

附錄十四.4,4’-bipyridine之紅外線光譜圖

4000 3000 2000 1000

Wavenumber (cm-1)

11121147117212511315134314161464149815681635

2027

2624

2710

287929693011

3128

No cm-1 %T Intensity 1 538.00 79.788 M 2 624.00 68.999 S 3 652.00 92.164 W 4 685.00 89.283 W 5 731.00 94.415 W 6 776.00 75.870 S 7 805.00 90.331 W 8 836.00 74.284 S

No cm-1 %T Intensity 9 923.00 74.709 S 10 967.00 75.062 S 11 1064.00 85.277 M 12 1085.00 87.368 M 13 1112.00 86.095 M 14 1147.00 73.839 S 15 1172.00 87.775 M 16 1251.00 70.694 S

No cm-1 %T Intensity 17 1271.00 76.911 S 18 1315.00 75.141 S 19 1343.00 69.009 S 20 1416.00 62.593 VS 21 1464.00 62.029 VS 22 1498.00 74.169 S 23 1568.00 77.130 S 24 1592.00 78.437 M

No cm-1 %T Intensity 25 1635.00 61.439 VS 26 2027.00 94.641 W 27 2624.00 81.624 M 28 2710.00 77.042 S 29 2879.00 69.863 S 30 2969.00 70.002 S 31 3011.00 69.444 S 32 3128.00 72.147 S

4000 3000 2000 1000

Wavenumber (cm-1)

%Transmittance 506580615677737811862

994

No cm-1 %T Intensity 1 506.00 53.639 S 2 580.00 59.457 M 3 615.00 50.188 S 4 677.00 59.308 M

No cm-1 %T Intensity 7 862.00 63.842 W 8 994.00 55.081 S 9 1044.00 61.341 M 10 1075.00 58.525 M

No cm-1 %T Intensity 13 1324.00 60.211 M 14 1413.00 54.084 S 15 1492.00 60.867 M 16 1531.00 56.782 M

No cm-1 %T Intensity 19 1684.00 62.805 M 20 1958.00 64.952 W 21 2351.00 63.711 W 22 2832.00 63.349 M

附錄十五.5,5’-bipyrimidine之紅外線光譜圖

4000 3000 2000 1000

Wavenumber (cm-1)

%Transmittance 3025 1571 1550 1400 1331 1196 1175 1141 1125 991 938 908 730 639 627

No cm-1 %T Intensity 1 627.00 72.817 M 2 639.00 65.728 M 3 730.00 63.795 S 4 908.00 77.086 W

No cm-1 %T Intensity 5 938.00 81.923 W 6 991.00 73.750 M 7 1060.00 81.935 W 8 1125.00 79.381 W

No cm-1 %T Intensity 9 1141.00 76.762 W 10 1175.00 70.208 M 11 1196.00 79.297 W 12 1331.00 71.105 M

No cm-1 %T Intensity 13 1400.00 49.894 VS 14 1550.00 69.341 M 15 1571.00 74.292 M 16 3025.00 77.949 W

附錄十六.5,5’-bipyrimidine之核磁共振光譜-氫譜

附錄十七.5,5’-bipyrimidine之質譜分析

在文檔中含L-組胺酸之掌性金屬錯合物之自組裝合成、結構多變性與性質研究 (頁 95-143)