臺灣博碩士論文加值系統

本論文分五部份探討含柔性雙醯胺雙吡啶與四芽羧酸基配位高分子的合成，結構與特性。
第一部分：此部份回顧了本實驗室在過去幾年在柔性雙醯胺雙吡啶的研究工作。這種配位基具有柔軟的-CH2-骨架與多樣性的鍵結模式，可經由氮原子或氧原子鍵結到金屬原子上，在合成配位高分子上具有重大的效益。我們將回顧以此配位基或加入羧酸配位基所合成的配位高分子的結構並探討此類配位基在配位高分子中的構型。
第二部分: 此部分報導了兩對的超分子異構物:[HgBr2(GAG-L1)]∞ [L1 = N,N-di(3-pyridyl)adipoamide] ， 1 ，[HgBr2(AAA-L1)]∞， 2 ， [HgI2(GAG-L1)]∞， 3 ，與 [HgI2(AAA-L1)]∞， 4。這四化合物以不同的方法製備，並以單晶繞射儀鑑定其結構。化合物1形成一個meso-helical的鏈狀化合物，化合物2與4為一維的螺旋狀化合物，而化合物3為sinusoidal鍊狀化合物。化合物1與3的L1配位機具有GAG trans syn-syn的構型，而在化合物2與4中具有AAA trans syn-syn的構型。化合物1與3在加熱或水熱的條件下可可逆地轉換為2與4。除此之外化合物1在固態中呈現較強的藍紫色的螢光，化合物2與3的藍綠螢光較弱，而化合物4偵測不到螢光。
第三部分:利用柔性配位基bis(3,5-dicarboxyphenyl)adipoamide， H4L6， bis(N-pyrid-3-ylmethyl)adipoamide， L4 與 bis(N-pyrid-3-ylmethyl) suberoamide， L5， 在水熱條件下可製備四個配位高分子{[M(L6)0.5(L4)(H2O)2]H2O}n (M = Co, 5; Ni, 6) 與{[M2(L6)(L5)2(H2O)4]3H2O}n (M = Co, 7; Ni, 8)。這些化合物的結構皆以單晶繞射儀鑑定。化合物5 - 8具有相同的拓譜學結構，皆屬2-fold交互穿透的三維結構，拓譜學名稱為moganite。除此之外，兩個Co(II)化合物在加熱去除溶劑後具變色的特性，且可進行可逆的轉換，但Ni(II)化合物不具此特性。此四化合物皆具良好的光降解能力，且Co(II)化合物效率較Ni(II)化合物為佳。
第四部分:利用柔軟的四芽羧酸bis(3,5-dicarboxyphenyl) adipoamide， H4L6 與其異構物，bis(2,5-dicarboxyphenyl)adipoamide ，H4L7，以水熱法製備了三個Mg(II)配位高分子[Mg2(L6)(H2O)2]2EtOH3H2O， 9 ，[Mg2(L6)(H2O)8] ， 10與 [Mg2(L7)(H2O)6]H2O， 11。其結構以單晶繞射儀鑑定。化合物9與10的形成與溶劑比例有關且皆為穩定的產物。化合物9的配位基形成獨特的8-nonadentate構型，為三維的結構，其拓譜學為(44.66)-pcu-5-Pmna，而化合物10與11的配位基分別形成4-tetradentate 與 6-hexadentate構型，其結構分別為一維鍊狀與具{4.62}2{42.610.83}-rtl拓譜學的三維結構。化合物9與10可進行一系列的可逆結構轉換，但化合物11的結構轉換則為不可逆。所有的化合物皆發生藍色的螢光，其中化合物11的強度較佳。
第五部分:利用三個柔軟的配位基bis(3,5-dicarboxyphenyl) adipoamide ，H4L6，N,N’-bis(3-pyridyl)sebacoamide，L2 與N,N’-bis(3-pyridyl)dodecanedipoamide， L3，以水熱法製備了四個配位高分子[Co(L6)0.5(H2O)3]H2O， 12， [Co(L6)0.5(L2)(H2O)]4H2O， 13， [Cd(L6)(H2O)2]2EtOH3H2O ，14 與 [HgI2(L3)]∞, 15。這些化合物的結構皆以單晶繞射儀鑑定。化合物12形成二維的環狀結構，其拓譜學為(4.62)2(42.62.82)，化合物13為二維結構，其拓譜學為{42.82.102}{42.84}2{4}2，化合物14為三維之結構，其拓譜學為(44.66)-pcu，而化合物15為一維的鏈狀結構。化合物12與13的熱分析亦將加以探討。

In this dissertation, the syntheses, structures and properties of coordination polymers based on the flexible bis-pyridyl-bis-amide and/or tetracarboxylate ligands, have been extensively discussed and summarized basically in five parts.
Part I: The contribution of flexible bis-pyridyl-bis-amide (bpba) ligands, which are also known as versatile ligands possessing various active coordination atoms (N and O) and different flexible –CH2– skeletons, is significant in the construction of coordination polymers. In this Highlight, structures of the different dimensional networks based on the flexible bpba ligands with or without participation of auxiliary polycarboxylate ligands are discussed, along with an overview of the preparations and conformations of the ligands.
Part II: Two pairs of Hg(II) supramolecular isomers, [HgBr2(GAG-L1)]∞ [L1 = N,N-di(3-pyridyl)adipoamide], 1, and [HgBr2(AAA-L1)]∞, 2, and [HgI2(GAG-L1)]∞, 3, and [HgI2(AAA-L1)]∞, 4, have been successfully synthesized by various methods, and structurally characterized by single crystal X-ray crystallography. Complex 1 forms a one-dimensional (1D) meso-helical chain, 2 and 4 exhibit normal 1D helical chains, while 3 displays a 1D sinusoidal chain. The L1 ligands in 1 and 3 display GAG trans syn-syn conformation, while those in 2 and 4 adopt the AAA trans syn-syn conformation. In addition, complexes 1 and 3 can be irreversibly transformed to 2 and 4, respectively, under simple heating or hydrothermal condition. Moreover, complex 1 exhibits intense violet-blue photoluminescence in the solid state, whereas 2 and 3 display weak broad emissions in the blue-green region and 4 shows undetectable emission intensity.
Part III: By utilizing the flexible ligands, bis(3,5-dicarboxyphenyl)adipoamide, H4L6; bis(N-pyrid-3-ylmethyl)adipoamide, L4; and bis(N-pyrid-3-ylmethyl) suberoamide, L5, four coordination polymers of the types {[M(L6)0.5(L4)(H2O)2]H2O}n (M = Co, 5; Ni, 6) and {[M2(L6)(L5)2(H2O)4]3H2O}n (M = Co, 7; Ni, 8) have been hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. Complexes 5 - 8 are topologically identical coordination polymers having the moganite type 2-fold interpenetrating 4,4-connected 3D net. Additionally, both Co(II) complexes are thermochromic and exhibit the reversible structural transformation on dehydration/rehydration followed by the color change but Ni(II) complexes are unable to show such behavior. All four complexes display good photo-degradation performance and the Co(II) complexes show slightly higher efficiencies than the Ni(II) ones.
Part IV: By using a new flexible tetracarboxylic acid, bis(3,5-dicarboxyphenyl) adipoamide, H4L6, and its isomer, bis(2,5-dicarboxyphenyl)adipoamide, H4L7, three Mg(II) coordination polymers, [Mg2(L6)(H2O)2]2EtOH3H2O, 9, [Mg2(L6)(H2O)8], 10, and [Mg2(L7)(H2O)6].H2O, 11, have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Complexes 9 and 10 are the solvent ratio dependent hydrothermally stable products. The tetracarboxylate ligand of complex 9 adopts a unique 8-nonadentate bonding mode, resulting in a three-dimensional (3D) 5-connected uninodal (44.66)-pcu-5-Pmna net, whereas those of 10 and 11 display the 4-tetradentate and 6-hexadentate bonding modes, forming a 1D linear chain and a 3,6-connected 2-nodal 3D net having {4.62}2{42.610.83}-rtl topology, respectively. Complex 9 shows a series of structural transformations on heating up to 200 oC and almost reversible structural transformation when the activated products were immersed in the mixture of ethanol and water or on hydrothermal. Likewise, complex 10 exhibits reversible structural transformation on heating/hydrothermal while 11 exhibits the irreversible structural transformations. All three complexes exhibit blue light emissions and that of complex 11 is much more intense.
Part V: By applying three flexible ligands, bis(3,5-dicarboxyphenyl) adipoamide, H4L6; N,N’-bis(3-pyridyl)sebacoamide, L2 and N,N’-bis(3-pyridyl)dodecanedipoamide, L3; four new coordination polymers: [Co(L6)0.5(H2O)3]H2O, 12; [Co(L6)0.5(L2)(H2O)]4H2O, 13; [Cd(L6)(H2O)2]2EtOH3H2O, 14 and [HgI2(L3)]∞, 15; have been hydrothermally synthesized and structurally characterized by the single crystal X-ray diffraction. Complex 12 forms the 2D looped like structure with (4.62)2(42.62.82) topology, while 13 possesses a 2,4,4-connected-3-nodal 2D net with the new topology {42.82.102}{42.84}2{4}2. Further, complex 14 possesses a three-dimensional (3D) 5-connected uninodal (44.66)-pcu net, whereas 15 displays a 1D linear chain. Moreover, the thermal properties of complexes 12-13 were investigated.

Contents
中文摘要 I
Abstract III
Acknowledgement VI
Contents VII
List of Tables XII
List of Figures XIII
List of Schemes XVII
List of ESI XVIII
CHAPTER 1 1
1.1 General Introduction 1
1.2 References 7
CHAPTER 2 9
2.1. Introduction 10
2.2. Preparation of bpba Ligands. 12
2.3. Preparation of CPs. 17
2.4. Dimensionality of the structures 17
2.4.1. Zero-dimensional compounds 18
2.4.2. One-dimensional CPs 19
2.4.3. Two-dimensional CPs 23
2.4.4. Three-dimensional CPs 28
2.5. Ligand Conformation 32
2.6. Bonding mode of the bpba ligands 34
2.7. Structural influence of halide anions 34
2.8. Supporting roles of auxiliary polycarboxylate ligands 35
2.8.1. Tuning the degree of interpenetration 36
2.8.2. Tuning the number of helices 37
2.8.3. Formation of versatile polycatenated networks 38
2.9. Ligand-isomerism controlled structural diversity 39
2.10. Effect of nature of solvents and ratio of reagents 41
2.11. Crystal-to-crystal transformation 42
2.12. Gas sorption 43
2.14. Summary 44
2.15 References 45
CHAPTER 3 53
3.1. Introduction 54
3.2. Experimental section 56
3.2.1. General procedures 56
3.2.2. Materials 56
3.2.3. Preparation 57
3.2.3.1. [HgBr2(GAG-L1)]∞, 1, and [HgBr2(AAA-L1)]∞, 2 57
3.2.3.2. [HgI2(GAG-L1)]∞, 3 58
3.2.3.3. [HgI2(AAA-L1)]∞, 4 58
3.2.4. X-ray crystallography 58
3.3. Results and Discussions 61
3.3.1. Crystal structures of 1 and 2 61
3.3.2. Crystal structures of 3 and 4 65
3.3.4. Structural transformation 68
3.3.5. Thermal Properties 71
3.3.6. Absorption and emission properties 71
3.4. Summary 75
3.5. Supporting Information Available: 75
3.6 References 76
CHAPTER 4 79
4.1. Introduction 80
4.2. Experimental section 83
4.2.1. General procedures. 83
4.2.2. Materials. 83
4.2.3. Preparations 84
4.2.3.1. Bis-(3,5-dicarboxyphenyl) adipoamide, H4L6 84
4.2.3.2. Bis(N-pyrid-3-ylmethyl)adipoamide, L4 84
4.2.3.3. Bis(N-pyrid-3-ylmethyl)suberoamide, L5 85
4.2.3.4. [Co(L6)0.5(L4)(H2O)2]H2O, 5 85
4.2.3.5. [Ni(L6)0.5(L4)(H2O)2]H2O, 6 86
4.2.3.6. [Co2(L6)(L5)2(H2O)4]3H2O, 7 86
4.2.3.7. [Ni2(L6)(L5)2(H2O)4]3H2O, 8 87
4.2.4. X-ray crystallography 87
4.2.5. Catalytic experimental activity 89
4.3. Results and Discussions 89
4.3.1. Crystal structures of 5 - 8 89
4.3.2. Ligand conformation 93
4.3.3. PXRD patterns and thermogravimetric analysis 94
4.3.4. Reversible structural transformation 95
4.3.5. Optical and thermochromic properties 99
4.3.6. Co(II) vs Ni(II) complexes 103
4.3.7. Photocatalytic Properties 103
4.4. Summary 107
4.5. Supporting Information Available: 108
4.6 References 108
CHAPTER 5 114
5.1. Introduction 115
5.2. Experimental section 117
5.2.1. General procedures. 117
5.2.2. Materials. 118
5.2.3. Preparation 118
5.2.3.1. Bis(2,5-dicarboxyphenyl)adipoamide, H4L7 118
5.2.3.2. [Mg2(L6)(H2O)2]2EtOH3H2O, 9 119
5.2.3.3. [Mg2(L6)(H2O)8], 10 120
5.2.3.4. [Mg2(L7)(H2O)6]H2O, 11 120
5.2.4. X-ray crystallography 121
5.3. Results and Discussions 123
5.3.1. Synthesis 123
5.3.2. Crystal structure of 9 123
5.3.3. Crystal structure of 10 126
5.3.4. Crystal structure of 11 128
5.3.5. Coordination modes and Ligand conformation 130
5.3.6. PXRD patterns and thermogravimetric analysis 132
5.3.7. Structural transformation 133
5.3.8. Absorption and luminescent properties 136
5.4. Summary 140
5.5. Supporting Information Available: 140
5.6 References 141
CHAPTER 6 147
6.1. Introduction 148
6.2. Experimental section 149
6.2.1. General procedures. 149
6.2.2. Materials. 150
6.2.3. Preparation of complexes 12-15 150
6.2.3.1. [Co(L6)0.5(H2O)3]H2O, 12 150
6.2.3.2. [Co(L6)0.5(L2)(H2O)]4H2O, 13 151
6.2.3.3. [Cd(L6)(H2O)2]2EtOH3H2O, 14 151
6.2.3.4. [HgI2(L3)]∞, 15 152
6.2.4. X-ray crystallography 152
6.3. Results and Discussions 154
6.3.1. Crystal structures of 12. 154
6.3.2. Crystal structures of 13. 156
6.3.3. Crystal structures of 14. 158
6.3.4. Crystal structure of 15. 161
6.3.5. Ligand conformation 163
6.3.6. PXRD patterns and TGA 164
6.4. Summary 165
6.5. Supporting Information Available: 165
6.6 Refernces 165
Conclusions 170
Electronic Supplementary Information (ESI) 172

List of Tables
Table 1. Sources for the preparation of the -NH-CO- type ligands. 15
Table 2. 0D compounds based on the –NH–CO– type bpba ligands. 18
Table 3. 1D CPs based on the –NH–CO– type bpba ligands. 20
Table 4. Two dimensional CPs based on the –NH–CO– type bpba ligands. 24
Table 5. Three dimensional CPs based on the –NH–CO– type bpba ligands. 29
Table 6. Crystal data for complexes 1 - 4. 59
Table 7. Selected bond distance (Å) and Angles (o) for complexes 1 – 4. 60
Table 8. Ligand conformations and corresponding angles for L1 in complexes 1 – 4. 68
Table 9. Crystal data for complexes 5 - 8. 88
Table 10. Calculation of band gaps (Eg) of 5- 8 by using the absorbance edge wavelength (nm). 100
Table 11. Crystal data for complexes 9 - 11. 122
Table 12. Solid state PL of Ligands (H4L6 and H4L7) and complexes (9 – 11) at room temperature. 137
Table 13. Crystal data for complexes 12 - 15. 153
Table 14. Ligand conformations in complexes 12 – 15. 164

List of Figures
Figure 1. Three possible orientations for the pyridyl nitrogen atoms of the L9 32
Figure 2. The twelve possible conformations for the L16 ligand. 33
Figure 3. A drawing representing anion-directed self-assembly of Zn(II) complexes and their transformations. 35
Figure 4. A schematic view of the twelve fold [6 + 6] interpenetration for 160. 36
Figure 5. The schematic views of 158, 159 and 166, showing the dia topology with 8- and 9-fold interpenetrating modes, and 3-fold framework with the pcu Zn2(COO)2 dimer decorated topology, respectively. 37
Figure 6. The schematic views illustrating the structural directing roles of polycarboxylate ligands. 38
Figure 7. The schematic views of 128, 164 and 165, illustrating the effect of angular dicarboxylate ligands on the degree of interpenetration of polycatenation Co(II) coordination networks. 39
Figure 8. A diagrammatic illustration of the structure of 155. 40
Figure 9. A diagrammatic representation of the structure of 144. 40
Figure 10. The schematic views of 152, 153 and 60. 41
Figure 11. The schematic view of 129 and 162 illustrating the effect of the nature of solvents in determining the structural diversity. 42
Figure 12. A drawing showing the reversible structural transformation between 55 (upper) and 58 (below). 43
Figure 13. (a) Coordination environment of 1. Symmetry Code: (A) –x + 1, y, –z + 3/2. (b) A view showing the 1D meso-helical structure. (c) A view of 1 on bc plane. 64
Figure 14. (a) Coordination environment of 2. Symmetry Code: (A) y, x, –z. (b) A view showing the helical chain. (c) A view of 2 on ab plane. 65
Figure 15. (a) Coordination environment of 3. Symmetry Code: (A) x, –y + 3/2, z. (b) A view showing sinusoidal polymeric chains. (c) A view of 3 on ac plane. 67
Figure 16. Variable temperature powder XRD patterns of 1 showing crystal to crystal transformation: (a) simulation of 1, (b) RT, (c) 120 oC, (d) 150 oC, (e) 170 oC, (f) 175 oC, (g) 180 oC, (h) 190 oC, (i) 210 oC and (j) simulation of 2. 70
Figure 17. Powder XRD patterns showing structural transformation from 3 to 4 under hydrothermal condition: (a) simulation of 3, (b) 3 as synthesized, (c) 3 after hydrothermal and (d) simulation of 4. 71
Figure 18. (a) Emission and excitation spectra of 1 - 3. (b) Images of crystals 1 - 4 under UV lamp at 365 nm in dark room. (c) Images of powder 1 - 4 under UV lamp at 365 nm in dark room. 75
Figure 19. (a) Coordination environment about the metal ion of 5 (M = Co) and 6 (M = Ni). Symmetry Code: (A) –x + 1,-y + 1,-z + 2. (b) Coordination environment of 7 (M = Co) and 8 (M = Ni). Symmetry Code: (A) x, y, z + 1. (c) A drawing showing the 1D chain formed by the µ4-linkage of (L6)4- ligand in 5 and 6. (d) A drawing showing the 1D chain formed by the µ4-linkage of (L6)4- ligand in 7 and 8. 92
Figure 20. (a) A drawing showing the 4,4-connected mog moganite 2-fold interpenetrating 3D framework of 5 – 8. (b) A drawing showing the single net of the two fold interpenetrating 3D framework. 93
Figure 21. (a) Variable temperature PXRD patterns of complex 5 with photograph showing reversible structural transformation followed by the color change. (b) Photographs of the activated powder of 5. 97
Figure 22. (a) Variable temperature PXRD patterns of complex 7 with photograph showing reversible structural transformation followed by the color change. (b) Photographs of the activated powder of 7. 98
Figure 23. Solid state diffuse-reflectance spectra of complexes 5 – 8 with BaSO4 as background. 99
Figure 24. Experimental evidence of reversible color change phenomena of complex 5 confirmed by absorbance edges obtained from the solid state UV-vis diffuse reflectance spectroscopy. 102
Figure 25. Thermochromism of complex 7 confirmed by the solid state UV-vis diffuse reflectance spectroscopy. 103
Figure 26. Photocatalytic degradation of MB solution under UV irradiation: (a) a plot of Ct/Co vs irradiation time. (b) A plot of degradation efficiency vs irradiation time. 106
Figure 27. (a) Coordination environment of 9; Symmetry Code: (A) –x + 3/2, y + 1/2, z + 1/2, (B) –x + 1, -y + 1, z + 1/2, (C) x, y + 1, z, (D) –x + 1, -y + 1, z - 1/2. (b) A view showing a dinuclear Mg2 unit as a 5-connected node. (c) 3D (44.66)- pcu-5-Pmna topological net of 9. 125
Figure 28. (a) Coordination environment of 10; Symmetry Code: (A) -x, -y, -z. (b) A view showing the 1D structure of 10. (c) A drawing showing π-π interaction, [3.6808(0) Å] in 10, resulting a 2D sheet. 127
Figure 29. (a) Coordination environment of 11; Symmetry Code: (A) -x, y - 1/2, -z + 1/2, (B) –x + 1, y - 1/2, -z + 1/2. (b) A view showing a Mg(II) unit as a 3-connected node. (c) 3D {4.62}2{42.610.83}-rtl topological net of 11. 129
Figure 30. Various coordination modes of tetracarboxylate ligands: (a) (L6)4- in 9 (b) (L6)4- in 10 (c) (L7)4- in 11. 131
Figure 31. (a) Variable temperature powder XRD patterns of 9 showing a series of stepwise structural transformations from 9 to 9a to 9b to 9c. (b) Powder XRD patterns showing reversible structural transformation from 9b or 9c to 9 by applying various methods. 135
Figure 32. Variable temperature powder XRD patterns of 10 showing reversible structural transformation. 136
Figure 33. Emission and excitation spectra of (a) H4L6, 9, 10, H4L7 and 11. (b) Images of powder 9-11 under UV lamp at 365 nm in a dark room. 139
Figure 34. (a) Coordination environment of 12. Symmetry Code: (A) –x, –y, –z+1 (B) –x, –y+1, –z+1. (b) A view showing the 2D loop-like structure of 12. (c) 2D (4.62)2(42.62.82) topological net of 12. 156
Figure 35. (a) Coordination environment of 13. Symmetry Code: (A) x, y–1, z (B) –x+1, –y+2, –z+1. (b) A view showing the 2,4,4-connected 3 nodal 2D structure of 13. (c) 2D {42.82.102}{42.84}2{4}2 topological net of 13. 158
Figure 36. (a) Coordination environment of 14; Symmetry Code: (A) x+1/2, –y+3/2, z , (B) –x+1, –y+1, z–1/2, (C) –x+1, –y+2, z–1/2, (D) x, y, z–1. (b) A view showing a dinuclear Mg2 unit as a 5-connected node. (c) 3D (44.66)- pcu-5-Pmna topological net of 14. 161
Figure 37. (a) Coordination environment of 15. Symmetry Code: (A) x, –y+1/2, –z+3/2. (b) A view showing 1D linear chain. (c) A drawing showing the N–H---O interactions in 15. 162

List of Schemes
Scheme 1. Schematic illustration of different structural diversities in the syntheses of coordination polymers. 1
Scheme 2. Schematic illustration for application of coordination polymers. 2
Scheme 3. Structure of organic linkers used for crystal syntheses. (a) L1 = N,N’-bis(3-pyridyl)adipoamide. (b) L2 = N,N’-bis(3-pyridyl)sebacoamide. (c) L3 = N,N’-bis(3-pyridyl)dodecanedipoamide. (d) L4 = N,N’-bis(3-pyridylmethyl) adipoamide. (e) L5 = N,N’-bis(3-pyridylmethyl)suberoamide. (f) H4L6 = bis(3,5-dicarboxyphenyl) adipoamide. (g) H4L7 = bis(2,5-dicarboxyphenyl)adipoamide. 4
Scheme 4. Reactions pathways for the syntheses of all complexes discussed in this thesis. 7
Scheme 5. Schematic presentation for the synthesis of –NH–CO– type ligands. 13
Scheme 6. Schematic presentation for the synthesis of semi-rigid –NH–CO– type ligands. 14
Scheme 7. Preparations and structural transformations for 1 - 4. 56
Scheme 8. Schematic drawing of the structures of various ligands: (a) H4L6, (b) L4 and (c) L5. 83
Scheme 9. Structures of flexible tetracarboxylate ligands: H4L6 (a) and H4L7 (b). 116
Scheme 10. Syntheses and transformations of complexes 9 - 11. 117
Scheme 11. Schematic drawing of the structures of ligands: (a) H4L6, (b) L2 and (c) L3. 149

List of ESI
Fig. S1. (a) A drawing showing the N–H---O interactions in 1. (b) A drawing showing the shortest π- π contact. 172
Fig. S2. (a) A drawing showing the N–H---O interactions in 2. (b) A drawing showing the shortest π- π contact. 173
Fig. S3. (a) A drawing showing the N–H---O interactions in 3. (b) A drawing showing the shortest π- π contact. 174
Fig. S4. (a) A drawing showing the N–H---O interactions in 4. (b) A drawing showing the shortest π- π contact. 175
Fig. S5. Simulated and experimental powder X-ray patterns for 1. 176
Fig. S6. Simulated and experimental powder X-ray patterns for 2. 176
Fig. S7. Simulated and experimental powder X-ray patterns for 1 (alternate method). 177
Fig. S8. Simulated and experimental powder X-ray patterns for 2 (alternate method). 177
Fig. S9. Simulated and experimental powder X-ray patterns for 3. 178
Fig. S10. Simulated and experimental powder X-ray patterns for 4. 178
Fig. S11. (a) Powder XRD pattern of 3 at variable temperature showing crystal to crystal transformation: (a) simulation of 3, (b) RT, (c) 180 oC, (d) 190 oC, (e) 200 oC (f) 210 oC and (g) simulation of 4. (b) Powder XRD patterns showing structural transformation from complex 1 to 2 under hydrothermal condition. 179
Fig. S12. DSC thermogram of complex 1. 181
Fig. S13. DSC thermogram of complex 2. 181
Fig. S14. DSC thermogram of complex 3. 182
Fig. S15. DSC thermogram of complex 4. 182
Fig. S16. Solid state UV/Visible spectra of 1- 4. 183
Fig. S17. (a) Solid and (b) solution (0.5 mM in DMF and EtOH) emission/excitation spectra of L1 ligand. 183
Fig. S18. Normalized emission spectra of 1-3 in the solid state. 184
Fig. S19. 1H NMR (DMSO-d6, 400 MHz) of H4L6. 185
Fig. S20. 13C NMR (DMSO-d6, 400 MHz) of H4L6. 185
Fig. S21. TOF, ESI-MS (methanol) of H4L6. 186
Fig. S22. A photograph showing the internal side of a black photodegradation box. 186
Fig. S23. Simulated and experimental powder X-ray patterns for 5. 187
Fig. S24. Simulated and experimental powder X-ray patterns for 6. 187
Fig. S25. Simulated and experimental powder X-ray patterns for 7. 188
Fig. S26. Simulated and experimental powder X-ray patterns for 8. 188
Fig. S27. TGA curves of 5-8 with activated samples of 5 and 7. 189
Fig. S28. Powder XRD patterns for activated 5 immersed in water for 5 days with photographs. 189
Fig. S29. Powder XRD patterns for activated 7 immersed in water for 5 days with photographs. 190
Fig. S30. Variable temperature powder XRD patterns for 6 with photographs. 190
Fig. S31. Variable temperature powder XRD patterns for 8 with photographs. 191
Fig. S32. Solid state UV-vis spectra of ligands: H4L6, L4 and L5. 191
Fig. S33. Solid state UV-vis spectra of complexes 5-8. 192
Fig. S34. UV-vis absorption spectra of the MB under UV irradiation. 192
Fig. S35. UV-vis absorption spectra of the MB solution under the UV irradiation in the presence of H2O2 along with (a) 5, (b) 6, (c) 7 and (d) 8. 195
Fig. S36. Photocatalytic degradation rates of MB under UV irradiation (Ct/Co vs irradiation time). 197
Fig. S37. Powder XRD pattern of 5 after photocatalysis process. 199
Fig. S38. Powder XRD pattern of 6 after photocatalysis process. 200
Fig. S39. Powder XRD pattern of 7 after photocatalysis process. 200
Fig. S40. Powder XRD pattern of 8 after photocatalysis process. 201
Fig. S41. Schematic diagram of the degradation mechanism of organic dyes on the surface of coordination polymer based photocatalyst. 201
Fig. S42. 1H NMR (DMSO-d6, 400 MHz) of H4L7. 205
Fig. S43. 13C NMR (DMSO-d6, 400 MHz) of H4L7. 205
Fig. S44. TOF, ESI-MS (methanol) of H4L7. 206
Fig. S45. Two Mg(II) metal centers acting as a 5-connected single node in 11. 206
Fig. S46. Simulated and experimental powder X-ray patterns for 9 (1st method). 207
Fig. S47. Simulated and experimental powder X-ray patterns for 9 and 10 (2nd method). 207
Fig. S48. Simulated and experimental powder X-ray patterns for 11. 208
Fig. S49. TGA curves of (a) 9-11. 209
Fig. S50. Variable temperature powder XRD patterns of 11 showing irreversible structural transformation. 209
Fig. S51. Solid state UV/Visible spectra of 9-11. 210
Fig. S52. Solution emission/excitation spectra of H4L6 ligand (0.5 mM) in (a) EtOH and (b) DMF. 210
Fig. S53. Solution emission/excitation spectra of H4L7 ligand (0.5 mM) in (a) EtOH and (b) DMF. 212
Fig. S54. Simulated and experimental powder X-ray patterns for 12. 215
Fig. S55. Simulated and experimental powder X-ray patterns for 13. 215
Fig. S56. Simulated and experimental powder X-ray patterns for 14. 216
Fig. S57. Simulated and experimental powder X-ray patterns for 15. 216
Fig. S58. TGA curves of 12 and 13. 217
Fig. S59. Variable temperatures powder patterns of 13. 217

Table S1. Selected bond distance (Å) and Angles (o) for complexes 5 – 8 202
Table S2. Selected bond distance (Å) and Angles (o) for complexes 9 – 11. 213
Table S3. Selected bond distance (Å) and Angles (o) for complexes 12 – 15. 218

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