臺灣博碩士論文加值系統

　　含尿素配位基N,N'-dicyclohexyl-N-isonicotinoylurea (DCIU)和N,N'-dicyclohexyl-N-nicotinoylurea (DCNU)已被合成並與金屬鹽類反應。
　　以DCIU配位基與二價金屬鈷和銅反應，可得到一系列含尿素配位基的金屬化合物CoBr2(DCIU)2(C2H5OH)2，1；CuCl2(DCIU)2， 2；[Cu(DCIU)4(H2O)](ClO4)2，3；CoI2(DCNU)2，6；{[Cu(DCIU)2(H2O)2] (NO3)2}n，7。此外以DCNU配位基與過渡金屬鹵化物反應可得到CuCl2(DCNU)2，4及CuBr2(DCNU)2，5。化合物 1 - 6 中，中性配位基DCIU及DCNU以單芽方式配位至金屬。而化合物 7 中，配位基DCIU以雙芽方式配位至金屬。
　　含有未配位的水分子在化合物 1 ，4 及 5 的晶體結構中扮演一個重要的角色，水分子以氫鍵連結含尿素化合物的官能基形成一維的鏈。而化合物 2 於晶體結構中未含有水分子，藉由尿素官能基間的氫鍵作用力形成二維結構。在化合物 3 中，陰離子藉由與CH及OH形成的氫鍵存在於主體形成的洞穴，其結構中有四個DCIU配位基佔據於赤道平面並有一個水分子配位在軸上，且DCIU配位基上的吡啶環配製成風車的型式。於化合物 6 中，由於碘原子的大小造成銅金屬扭曲的四面體構型。化合物 7 中，雙芽配位基DCIU經由羰基的氧原子與吡啶環上的氮原子配位形成新穎的十四圓環的一維高分子鏈。

　　A series of compounds containing the urea ligands N,N'-dicyclohexyl -N-isonicotinoylurea, DCIU, and N,N'-dicyclohexyl-N-nicotinoylurea, DCNU, have been synthesized, and their structures characterized by single crystal X-ray crystallography.
　　The reactions of DCIU with transition metal salts of Co(II) and Cu(II) afforded CoBr2(DCIU)2(C2H5OH)2, 1, and CuCl2(DCIU)2, 2, and [Cu(DCIU)4(H2O)](ClO4)2, 3, CoI2(DCNU)2, 6, {[Cu(DCIU)2(H2O)2](NO3)2}n, 7, while the reactions of DCNU with transition metal halide complexes afforded CuCl2(DCNU)2, 4, and CuBr2(DCNU)2, 5. The neutral DCIU and DCNU ligands in complexes 1 - 6 are coordinated to the metal centers in monodentate fashions, while the DCIU in complex 7 is coordinated to the metal centers in bidentate fashions.
　　In the crystal structures of 1, 4 and 5, the discrete water molecules play an important role in forming the hydrogen bondings which link the molecules of the complexes to form 1-D chains. There is no water molecule inside the crystal structures of 2, and the extended hydrogen-bonding is generated via a combination of the urea functional groups to from 2-D structure. In complex 3, the anions reside within the central cavity of the host species, held by hydrogen bonds from both CH and OH donors. The four DCIU ligands occupy the equatorial plane, while the water molecule occupies one of the axial sites, and pyridine rings of the DCIU ligands are arranged in a windmill fashion. In the complex 6, the copper metal center adopts a distorted tetrahedral coordination geometry, owing to the size of iodide atom. In complex 7, the bidentate DCIU ligands coordinated to metal via oxygen atoms of carbonyl and nitrogen atoms of pyridyl rings, forming novel 1D polymer chains consisting of fourteen-membered metallocycles.

Contents

Chinese abstract I
English abstract II
Acknowledgement III
Contents IV
Scheme and Table contents V
Figure contents VI
Introduction 1
Experimental section 10
X-ray crystallography 16
Results and discussions 24
Conclusions 62
References 63
Appendix 67

Scheme and Table contents

Scheme 1. The reaction pathways of ligands DCIU and DCNU. 24
Scheme 2. The reaction pathways of complexes 1 – 7. 25

Table 1. Properties of strong, moderate and weak hydrogen bonds. 5
Table 2. Crystal data and structure refinement for DCIU and 1 - 7. 16
Table 3. Characteristic IR absorptions (cm-1) of the free ligands DCIU,
DCNU and complexes 1 – 7. 26
Table 4. Hydrogen bonding distances (Å) and angles (º) for the DCIU. 27
Table 5. Selected bond distances (Å) and angles (°) for CoBr2(DCIU)2(C2H5OH)2, 1. 32
Table 6. Hydrogen bonding distances (Å) and angles (º) for the 1. 32
Table 7. Hydrogen bonding distances (Å) and angles (º) for the 2. 35
Table 8. Selected bond distances (Å) and angles (°) for 2, 4, 5. 36
Table 9. Hydrogen bonding distances (Å) and angles (º) for the 3. 41
Table 10. The geometry, selected bond distances(Å) and angles(°) and dihedral angle(°) for Copper complexes. 42
Table 11. Hydrogen bonding distances (Å) and angles (º) for the 4, 5 47
Table 12. Selected bond distances (Å) and angles (°) for 6 54
Table 13. Hydrogen bonding distances (Å) and angles (º) for the 6 54
Table 14. Selected bond distances (Å) and angles (°) for 7 58
Table 15. Hydrogen bonding distances (Å) and angles (º) for the 7 58


Figure contents

Figure 1. Supramolecular ion-ion interactions exemplified by the interaction
of the organic cation [tris(diazabicyclooctane)]3+ with anion such as Fe(CN)63-.
2
Figure 2. The ion-dipole interactions of crown ether complex. 2
Figure 3. Two types of dipole-dipole interactions in carbonyls. 2
Figure 4. Base pairing in DNA by hydrogen bonding. 3
Figure 5. Schematic of the cation-π interaction. 3
Figure 6. Limiting types of π-π stacking. 3
Figure 7. The typical van der Waals inclusion complex p-tert-butylcalix[4]
arene • xenon. 4
Figure 8. View the organic guests which have hydrophobic effects in the aqueous solutions. 4
Figure 9. The structures of urea. 6
Figure 10. Hydrogen-bonding molecules, ureas, and oxalamides. 7
Figure 11. A series of the ureas for the symmetric ligands. 7
Figure 12. The urea•••X-M hydrogen-bonded synthon (R = any alkyl or aryl group). 8
Figure 13. Selective anion encapsulation by competitive crystallization of MOFs. 8
Figure 14. Intercalation of sulfate via eight hydrogen bonds from four urea groups. 9
Figure 15.The pyridyl of urea ligands DCIU and DCNU. 9
Figure 16. Molecular drawing of free ligand DCIU. 29

Figure 17. The view of the packing diagram for four molecules with intermolecular interaction. 29
Figure 18. Molecular structure showing the hydrogen bonds between the urea ligand and water molecule. 30
Figure 19. Molecular drawing of CoBr2(DCIU)2(C2H5OH)2 • 2H2O, 1. 32
Figure 20. The view of the packing diagram for CoBr2(DCIU)2(C2H5OH)2 • 2H2O, 1. Expanded hydrogen bonds packing diagram for 1. 33
Figure 21. Molecular structure showing the hydrogen bonds between the urea ligand and water molecule. 34
Figure 22. Molecular drawing of CuCl2(DCIU)2, 2. 37
Figure 23. The view of the packing diagram for CuCl2(DCIU)2, 2. 38
Figure 24. The view of the hydrogen bonds for CuCl2(DCIU)2, 2. 39
Figure 25. Molecular drawing of [Cu(DCIU)4(H2O)](ClO4)2, 3. 41
Figure 26. The packing diagram for [Cu(DCIU)4(H2O)](ClO4)2, 3, showing the interactions among the bonded water molecules, the discrete ClO4 – anions and the urea ligands. 43
Figure 27. (a) The view of the packing diagram for 3 along the c axis which compact and well organized the 2-D structures. 44
Figure 28. (a) Displays the orientation of Cu-OH2 are towards up and down along the b axis (Blue is aqua ligand towards the b axis, and the red is opposite.). 45
Figure 29. Molecular drawing of CuCl2(DCNU)2, 4. 47
Figure 30. The view of the packing diagram for CuCl2(DCNU)2 • 2H2O, 4. along the a axis. 48
Figure 31. Molecular drawing of CuBr2(DCNU)2 • 2H2O, 5. 50
Figure 32. The view of the packing diagram for CuBr2(DCNU)2 • 2H2O, 5.
along the a axis 51
Figure 33. (a) Expanded hydrogen bonds packing diagram for CuBr2(DCNU)2
•2H2O, 5 along the a axis. 52
Figure 34. Molecular drawing of CoI2(DCNU)2, 6. 54
Figure 35. (a) Expanded hydrogen bonds packing diagram for 6 along the a
axis, (b) along the c axis. 55
Figure 36. The view of the packing diagram for 6 along the b axis. 56
Figure 37. (a) Molecular drawing of {[Cu(DCIU)2(H2O)2](NO3)2}n, 7. (b) View of the 1-D arrays of the metalloligand poylmers of 7 within
the π-π interactions. 59
Figure 38. (a) The packing diagram for 7, showing the interactions among the bonded aqua ligands, the discrete NO3– anions and the urea ligands. 60
Figure 39. (a) The discrete NO3– anions are shown in space-filling mode. (b) Expanded the hydrogen bonds packing diagram for 7 along the a axis. 61

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