METAL COMPLEXES OF N-(7-HYDROXY-4-METHYL-8COUMARINYL)-AMINO ACID, N-(2-PYRIDYLMETHYL)AMINO ACID AND RELATED LIGANDS: SYNTHESIS, STRUCTURAL, PHOTOPHYSICAL AND GELATION PROPERTIES LEONG WEI LEE (B. Sc.,Universiti Teknologi Malaysia) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY NATIONAL UNIVERSITY OF SINGAPORE 2008 Acknowledgement I would like to express my sincerest appreciation to my supervisor, Professor Jagadese J. Vittal for his guidance, continuous support, encouragement and inspiration during these years. His valuable guidance helped me to proceed in the course of this project. His intellectual support and encouragement were indispensable for completion in this project. I am grateful to my collaborator, Professor Stefan Kasapis and Ms. Koh Lee Wah for rheological studies. I am thankful to Dr. Xu Qing-Hua and Mr. Lakshminarayana Polavarapu for fluorescence lifetime measurements. Special thanks to Professor Vivian Wing-Wah Yam and Mr. Anthony Yiu-Yan Tam, The University of Hong Kong, for the photophysical studies. Their help and contribution were essential in this work. I am thankful to all my group members for their moral support and advices. Particularly, I would like to express my gratitude to Dr. Ng Meng Tack, Dr. Tian Lu, Dr. Bellam Sreenivasulu, Dr. Sudip K. Batabyal and Dr. Mangayarkarasi Nagarathinam for their invaluable support, suggestions and motivation. Special thanks to Dr. Sudip K. Batabyal for his inspiration and contribution in the hydrogel projects. Deeply thanks to all the staffs in CMMAC laboratories and general office for their assistance during these years. I would like to thank Associate Professor Jagadese J. Vittal, Ms. Tan Geok Kheng and Professor Koh Lip Lin for their help in X-ray crystallography data collection and structure solution. I would like to thank all of my friends especially Jiang Jianming, Han Yuan and Pauline Ong for their moral support. I am grateful to my family for their love and understanding. Their encouragement is great motivation to me all the times. Lastly, I thank National University of Singapore for research scholarship. I Declaration This work described in this thesis was carried at the Department of Chemistry, National University of Singapore from 10th Jan 2005 to 31st Dec 2008 under the supervision of Associate Professor Jagadese J. Vittal. All the work described herein is my own, unless stated to the contrary, and it has not been submitted previously for a degree at this or any other university. Leong Wei Lee 31st December 2008 II Table of Contents Acknowledgements I Declaration II Table of Contents III Abbreviations Summary VIII X List of Compounds Synthesized XII List of Figures XXI List of Tables XXVIII Publications and Presentations XXX Chapter Introduction 1-1. Supramolecular chemistry and Crystal engineering 1-2. Supramolecular interactions 1-2-1. Hydrogen bonds 1-2-2. p-p interactions 1-3. Schiff base and reduced Schiff base from amino acids 1-3-1. N-(2-hydroxybenzyl)-amino acids 1-3-2. N-(2-pyridylmethyl)-amino acid ligands 14 1-4. Complexes of coumarin derivatives 19 1-5. Supramolecular gels 20 1-5-1. Hydrogels 21 1-5-2. Metallo- and coordination polymeric gels 22 1-6. Scope of the current investigation 29 Chapter Coordination Chemistry of Metal Complexes of Calcein Blue: 32 Monomeric, Ion-pair and Polymeric Complexes Preface to Chapter 33 III Part A Synthesis and Characterization of Metal Complexes of Calcein 34 Blue: Formation of Monomeric, Ion-pair and Coordination Polymeric Structures 2-A-1. Introduction 35 2-A-2. Results and discussion 37 2-A-2-1. Synthesis 37 2-A-2-2. Description of crystal structures 37 2-A-2-2-1. [Cu(Hmuia)(H2O)]×CH3OH×2H2O, IIA-1 37 2-A-2-2-2. [Ni(Hmuia)(H2O)2]×2H2O, IIA-2 39 2-A-2-2-3. [Mn(H2O)6][Mn2(muia)2(H2O)2]×2CH3CN, IIA-3 42 and [Mg(H2O)6][Mg2(muia)2(H2O)2]×2CH3CN, IIA-4 2-A-2-2-4. [Mn(H2O)4.5(CH3OH)1.5]2[{Mn2(muia)2}- 45 {Mn2(muia)2(H2O)2}]×5H2O, IIA-5 2-A-2-2-5. [Zn(H2O)5][Zn2(muia)2(H2O)2], IIA-6 49 2-A-2-3. Infrared studies 53 2-A-2-4. UV-vis absorption studies 54 2-A-2-5. Thermogravimetric and ESI-MS studies 55 2-A-2-6. Solid-state fluorescence studies 57 2-A-3. Summary 59 Part B Self-Assembly of Ion-Pair Complexes: One-pot Crystallization 60 and Pseudosupramolecular Isomerism 2-B-1. Introduction 61 2-B-2. Results and discussion 63 2-B-2-1. Synthesis 63 2-B-2-2. Description of crystal structures 63 2-B-2-2-1. [Co(H2O)4(CH3CN)2][Co(muia)(H2O)2]2, IIB-1 63 2-B-2-2-2. [Co(H2O)6][Co2(muia)2(H2O)2]×2CH3CN, IIB-2 66 2-B-2-2-3. [{Co(H2O)4}{Co2(muia)2(H2O)2}]×11H2O, IIB-3 69 2-B-2-3. Infrared studies 73 IV 2-B-2-4. UV-vis absorption studies 74 2-B-2-5. Thermogravimetric and ESI-MS studies 75 2-B-3. Summary 76 Part C Experimental section 78 2-C-1. Synthesis of complexes 78 2-C-2. X-ray crystallography 81 Chapter Complexes of N-(7-hydroxy-4-methyl-8-coumarinyl)-amino 82 acid as Novel Functional Crystalline and Gel Materials Preface to Chapter 83 Part A Metal Complexes of Coumarin Derivatized Amino Acid: Towards 84 Crystalline Materials 3-A-1. Introduction 85 3-A-2. Results and discussion 86 3-A-2-1. Synthesis 86 3-A-2-2. Description of crystal structures 86 3-A-2-2-1. H2mugly, III-a 86 3-A-2-2-2. H2muala, III-b 90 3-A-2-2-3. [Cu2(muala)2(H2O)2]·2H2O, IIIA-2 92 3-A-2-2-4. [Ni7(mugly)6(OH)6Na6(H2O)6]×20H2O, IIIA-4 95 3-A-2-2-5.[Ni4(mugly)4(H2O)2(m2-CH3COO)K2(H2O)4(EtOH)]×- 98 H2O×EtOH, IIIA-7 3-A-2-2-6. [Ni5(muala)2(m2-CH3COO)4(OH)2(H2O)4]×2.75H2O- 101 ×0.5DMF, IIIA-8 3-A-2-2-7. [Zn(muala)(H2O)]×0.5H2O, IIIA-10 104 3-A-2-2-8. [Zn(Hmuser)(H2O)]×0.5H2O, IIIA-11 108 3-A-2-3. Infrared studies 109 3-A-2-4. UV-vis absorption studies 111 V 3-A-2-5. Fluorescence studies 115 3-A-2-6. Thermogravimetric and ESI-MS studies 117 3-A-3. Summary 121 Part B Hydrogelation of Fluorescent Zinc(II) Coordination Polymer: 123 Synthesis, Photophysical and Gelation Properties 3-B-1. Introduction 124 3-B-2. Results and Discussion 125 3-B-2-1. Synthesis and properties of hydrogel 125 3-B-2-2. Microscopic morphological studies 126 3-B-2-3. UV-vis absorption studies 127 3-B-2-4. Fluorescence studies 131 3-B-2-5. Rheological studies 136 3-B-3. Summary 141 Part C Gelation-induced Fluorescence Enhancement of Amorphous 143 Magnesium(II) Coordination Polymeric Hydrogel 3-C-1. Introduction 144 3-C-2. Results and discussion 145 3-C-2-1. Synthesis and properties of hydrogel 145 3-C-2-2. Microscopic morphological studies 148 3-C-2-3. UV-vis absorption studies 150 3-C-2-4. Fluorescence studies 153 3-C-2-5. Rheological studies 158 3-C-3. Summary 164 Part D Experimental Section 166 3-D-1. Synthesis of ligands 166 3-D-2. Synthesis of complexes 167 3-D-3. Synthesis of hydrogels 174 3-D-4. X-ray crystallography 175 VI Chapter Coordination Polymers of Copper(II) Complexes of Reduced 176 Schiff Base Ligands, N-(2-pyridylmethyl)-amino acids: Synthesis, Structures and Characterization 4-1. Introduction 177 4-2. Results and Discussion 178 4-2-1. Synthesis 178 4-2-2. Description of crystal structures 180 4-2-2-1. [Cu(Pbals)(H2O)2]×ClO4×H2O, IV-1 180 4-2-2-2. [Cu(Pbal)(ClO4)(H2O)], IV-2 183 4-2-2-3. [Cu2(Paes)2(ClO4)2]×2H2O, IV-3 185 4-2-2-4. [Cu(Pae)(DMF)(H2O)]×ClO4IV-5a 188 4-2-2-5. [Cu(Pae)2]×2H2O, IV-6 190 4-2-2-6. [Cu(HPser)(CH3COO)], IV-8 192 4-2-3. Infrared studies 195 4-2-4. UV-vis absorption studies 196 4-2-5. Thermogravimetric and ESI-MS studies 198 4-3. Summary 200 4-4. Experimental 202 4-4-1. Synthesis of ligands 202 4-4-2. Synthesis of complexes 204 4-4-3. X-ray crystallography 207 Chapter Conclusion and Future Work 208 5-1. Summary of the present work 208 5-2. Suggestions for future work 212 References 214 Appendix 228 A1. Chemicals and Physicochemical Methods 228 A2. Crystallographic data and structure refinement details 232 A3. Copyright permission 237 A4. Typical spectroscopic data of compounds 238 A5. Curriculum vitae 244 VII Abbreviations 1D 2D 3D 2,2’-bpy 4,4’-bpy Anal. Calcd. CP gels d Decomp. DMF DNA dt EDTA e.s.d ESI-MS EtOH Et2O fac FESEM h H2muala H2mugly H3muia H3muser HPae HPaes HPala HPbal HPbals H2Pglu HPgly HPhis H2Pser H2Sae H2Sala H2Sbal H2ClSala H2MeSala H2Scp11 H2Sgly H3Sglu H2Shis H2Sval one dimensional two dimensional three dimensional 2,2’-bipyridine 4,4’-bipyridine analysis calculated coordination polymeric gels doublet decomposition dimethylformamide deoxyribonucleic acid doublet of triplet ethylenediaminetetraacetic acid estimated standard deviation (standard uncertainty parameter) electrospray ionization mass spectroscopy ethanol diethyl ether facial field emission scanning electron microscopy hour N-(7-hydroxy-4-methyl-8-coumarinyl)-L-alanine N-(7-hydroxy-4-methyl-8-coumarinyl)-glycine 4-methylumbelliferone-8-methyleneiminodiacetic acid / Calcein Blue N-(7-hydroxy-4-methyl-8-coumarinyl)-L-serine N-2(-pyridylmethyl)-aminoethanesulfonic acid N-(2-pyridylmethylene)-aminoethanesulfonic acid N-2(-pyridylmethyl)-L-alanine N-2(-pyridylmethyl)-b -alanine N-(2-pyridylmethylene)-b-alanine N-(2-pyridylmethyl)-L-glutamic acid N-(2-pyridylmethyl)-glycine N-(2-pyridylmethyl)-L-histidine N-(2-pyridylmethyl)-L-serine N-(2-hydroxybenzyl)-aminoethanesulfonicacid N-(2-hydroxybenzyl)-L-alanine N-(2-hydroxybenzyl)-b -alanine N-(2-hydroxy-5-chlorobenzyl)-L-alanine N-(2-hydroxy-5-methylbenzyl)-L-alanine N-(2-hydroxybenzyl)-1-aminocyclopentatecarboxylic acid N-(2-hydroxybenzyl)-glycine N-(2-hydroxybenzyl)-L-glutamic acid N-(2-hydroxybenzyl)-L-histidine N-(2-hydroxybenzyl)-L-valine VIII Hz IR LMCT m max M Me mer MeOH MLCT nm mp NMR phen ppm s SAFIN t temp TEM TG UV UV-vis wt % XRPD hertz infra red ligand to metal charge transfer multiplet maximum metal methyl meridional methanol metal to ligand charge transfer nanometer melting point nuclear magnetic resonance 1,10-phenanthroline parts per million singlet self-assembled fibrillar networks triplet temperature Transmission electron microscopy thermogravimetric analysis ultraviolet ultraviolet-visible weight percentage X-ray powder diffraction IX Appendix wavelength of 450 nm. The system gives a temporal resolution of ~100 ps. The measurements were performed by Dr. Xu Qinghua and Mr. Lakshminarayana, Department of Chemistry, National University of Singapore. X-ray powder diffraction The X-ray powder diffraction of the samples were recorded using a D5005 Bruker AXS diffractometer with Cu-Kα radiation (λ = 1.5410). Electron Microscopy Field emission scanning electron microscopy (FESEM) images were taken using a Jeol JSM-6700F field emission scanning electron microscope operated at kV and 10 mA. High resolution transmission electron microscopy (TEM) images and electronic diffraction patterns were obtained from a JEOL JSM-3010 instrument. Rheological measurements Rheological measurements were carried out on freshly prepared gels using a controlled stress rheometer (AR-1000N, TA Instruments Ltd., New Castle, DE, USA). Parallel plate geometry of 40 mm diameter and 1.5 mm gap was employed throughout. Following loading, the exposed edges of samples were covered with a silicone fluid from BDH (100 cs) to prevent water loss. Dynamic oscillatory work kept a frequency of rad s-1. The following tests were performed: increasing amplitude of oscillation up to 200% apparent strain on shear, time and frequency sweeps at 25°C (60 and from 0.1 to 100 rad s-1, respectively), and a heating run to 90°C at a scan rate of 1°C min-1. Unidirectional shear routines were performed at 25°C covering a shear-rate regime between 10-1 and 103 s-1. Mechanical spectroscopy routines were completed with transient measurements. In doing so, the desired stress was applied instantaneously to the sample and the angular displacement was monitored for 60 (retardation curve). After completion of the run, the imposed stress was withdrawn and the extent of structure recovery was recorded for another 60 (relaxation curve). Dynamic and steady shear measurements were conducted in triplicate and creep (transient) measurements in duplicate. 230 Appendix Single crystal X-ray crystallography The diffraction experiments were carried out on a Bruker AXS SMART CCD diffractometer with MoKα ((λ = 0.71073 Å) sealed tube. The program SMART285 was used for collecting frames of data, indexing reflection and determination of lattice parameters, SAINT286 for integration of the intensity of reflections and scaling, SADABS287 for absorption correction and SHELXTL288 for space group and structure determination, least-squares refinements on F2. The space groups were determined from the systematic absences and their correctness was confirmed by successful solution and refinement of structures. All the non-hydrogen atoms were refined anisotropically. All the C-H hydrogen atoms were placed in calculated positions. All the hydrogen atom positions of amine groups and water molecules were located and their positional parameters were refined in the least-squares cycles. All the single crystal X-ray diffraction experiments and refinements of the structural models have been carried out by Prof. Jagadese J. Vittal and Ms. Geok Kheng Tan, X-ray Diffraction Laboratory, CMMAC, Department of Chemistry, NUS. Additional crystallographic data in the form of CIF files are provided as a soft copy in the CD-ROM attached with this thesis. 231 A2. Crystallographic data and structure refinement details Table A1. Crystallographic data and structure refinement details (Chapter 2) Compound IIA-1 Formula C16H23CuNO11 Formula weight 468.89 Temperature (K) 298(2) Crystal system Monoclinic Space group P21/c a (Å) 11.7256(8) b (Å) 10.0987(7) c (Å) 17.2447(11) 90 a (°) 109.758(2) b (°) 90 g (°) V (Å3) 1921.8(2) Z 1.198 m (mm-1) Dcalc (mg m-3) 1.621 Reflections collected 11018 Independent reflections 3388 Rint 0.0261 Data/restraints/parameters 3388/15/290 Goodness-of-fit on F2 1.061 a 0.0460 Final R [I > 2s (I)], R1 wR2b 0.1283 a R1 = S||Fo| - |Fc||/S|Fo|. b wR2 = [Sw(Fo2 - Fc2)2/Sw(Fo2)2]1/2 IIA-2 C15H21NNiO11 450.04 223(2) Orthorhombic Pbca 7.6635(4) 14.9271(8) 30.9415(16) 90 90 90 3539.5(3) 1.160 1.689 18933 3104 0.0304 3104/42/289 1.277 0.0418 0.0943 IIA-3 C34H46Mn3N4O22 1027.57 223(2) Monoclinic P21/c 11.0327(4) 11.2261(4) 17.5320(7) 90 97.8710(10) 90 2150.95(14) 0.955 1.587 12397 3780 0.0228 3780/2/319 1.141 0.0529 0.1214 IIA-4 C34H46Mg3N4O22 935.68 223(2) Monoclinic P21/c 10.9130(12) 11.2227(11) 17.0764(16) 90 95.372(3) 90 2082.2(4) 0.164 1.492 11879 3662 0.0394 3662/8/321 1.240 0.0805 0.1671 IIA-5 C63H92Mn6N4O47 1987.05 223(2) Triclinic Pī 11.0083(7) 12.5277(9) 16.1039(10) 91.777(2) 108.46(2) 100.321(2) 2063.3(2) 0.994 1.599 12214 7255 0.0390 7255/22/595 1.076 0.0731 0.1672 232 Table A1. Continued… IIA-6 C30H38N2O21 Zn3 958.73 233(2) Monoclinic C2/c 16.9154(9) 11.1158(6) 21.7633(12) 90 108.6700(10) 90 3876.8(4) 1.926 1.643 10230 3313 0.0321 3313/51/292 1.067 0.0519 0.0674 Formula Formula weight T (K) Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) g (°) V (Å3) Z m (mm-1) Dcalc (mg m-3) Reflections collected Independent reflections Rint Data/restraints/parameters Goodness-of-fit on F2 Final R [I > 2s (I)], R1a wR2b a R1 = S||Fo| - |Fc||/S|Fo|. b wR2 = [Sw(Fo2 - Fc2)2/Sw(Fo2)2]1/2 IIB-1 C34H46Co3N4O22 1039.54 223 (2) Triclinic Pī 7.3060 (4) 12.8343 (6) 12.8921 (6) 114.592 (1) 104.129 (1) 97.066 (1) 1030.8 (9) 1.267 1.675 11206 3646 0.0315 3646/62/320 1.057 0.0331 0.0909 IIB-2 C34H46Co3N4O22 1039.54 223 (2) Monoclinic P21/c 10.8816 (6) 11.2074 (7) 17.248 (1) 90 96.281 (1) 90 2090.9 (2) 1.285 1.651 16342 4792 0.0382 4792/8/312 1.032 0.0471 0.1049 IIB-3 C30H58Co3N2O31 1119.57 223 (2) Triclinic Pī 7.3992 (5) 12.6509 (8) 13.2265 (9) 103.325 (1) 91.767 (1) 94.634 (2) 1199.26 (14) 1.122 1.506 6886 4192 0.0189 4192/3/370 1.064 0.0395 0.1085 233 Table A2. Crystallographic data and structure refinement details (Chapter 3) Compound III-a Formula C13H15NO6 Formula weight (g M-1) 281.26 Temperature (K) 223(2) Crystal system Monoclinic Space group P21/c a (Å) 11.6019(13) b (Å) 15.159(2) c (Å) 7.5024(9) 90 a (°) 103.930(3) b (°) 90 g (°) V (Å ) 1280.7(3) Z -1 0.117 m (mm ) Dcalc (mg m-3) 1.459 Reflections collected 8861 Independent reflections 2927 Rint 0.0492 Data/restraints/parameters 2927/2/197 Goodness-of-fit on F 1.026 0.0846 Final R [I > 2s (I)], R1a wR2b 0.2103 Absolute structure -parameter a R1 = S||Fo| - |Fc||/S|Fo|. b wR2 = [Sw(Fo2 - Fc2)2/Sw(Fo2)2]1/2 III-b C14H15NO5 27727 223(2) Triclinic P1 5.3583(5) 5.8497(6) 10.4352(10) 88.144(2) 75.461(2) 82.331(2) 313.78(5) 0.112 1.467 3256 1669 0.0066 1669/3/184 1.070 0.0389 0.1007 0.3(12) IIIA-2 C28H34Cu2N2O14 749.65 223(2) Orthorhombic P212121 7.4813(8) 14.0424(13) 28.503(3) 90 90 90 2994.4(5) 1.496 1.663 17827 5893 0.0689 5893/10/443 1.077 0.0689 0.1496 0.07(2) IIIA-4 C78H66N6Na3Ni7O47 2319.31 223(2) Triclinic R3 15.4367(9) 15.4367(9) 35.721(4) 90 90 120 7371.6(10) 1.421 1.567 12786 2863 0.0848 2863/1/232 0.925 0.0793 0.2132 -- 234 Table A2. Continued… Compound IIIA-7 Formula C33.6H54KN2Ni2O21 Formula weight (g M-1) 978.51 Temperature (K) 223(2) Crystal system Monoclinic Space group P21/c a (Å) 22.5549(16) b (Å) 12.9601(9) c (Å) 15.0085(10) 90 a (°) 105.823(2) b (°) 90 g (°) V (Å3) 4221.0(5) Z 1.074 m (mm-1) Dcalc (mg m-3) 1.540 Reflections collected 29384 Independent reflections 9687 Rint 0.0444 Data/restraints/parameters 9687/12/617 Goodness-of-fit on F2 1.040 0.0488 Final R [I > 2s (I)], R1a wR2b 0.1211 Absolute structure parameter -a R1 = S||Fo| - |Fc||/S|Fo|. b wR2 = [Sw(Fo2 - Fc2)2/Sw(Fo2)2]1/2 IIIA-8 C39H59N3Ni5O30.5 1351.44 223(2) Orthorhombic C2221 13.9467(5) 26.2945(10) 16.3610(6) 90 90 90 5999.9(4) 1.496 1.496 21518 6891 0.0548 6891/17/379 1.030 0.0473 0.1172 0.020(17) IIIA-10 C14H16NO6.5Zn 367.65 223(2) Trigonal P3221 9.0773(5) IIIA-11 C14H15NO7.5Zn 382.64 223(2) Trigonal P3221 9.0174(3) 31.015(3) 90 90 90 2213.2(3) 1.698 1.665 15805 3802 0.0528 3802/0/214 1.094 0.0425 0.0895 0.006(15) 31.642(2) 90 90 90 2228.24(18) 1.695 1.711 15933 3404 0.0545 3404/0/227 1.032 0.0390 0.0879 -0.005(16) 235 Table A3. Crystallographic data and structure refinement details (Chapter 4) Compound IV-1 Formula C9H15ClCuN2O9 Formula weight (g M-1) 394.22 Temperature (K) 223(2) Crystal system Monoclinic Space group P21/c a (Å) 12.8651(14) b (Å) 7.4508(8) c (Å) 15.8758(18) 101.305(2) b (°) V (Å ) 1492.3(3) Z -1 1.689 m (mm ) Dcalc (mg m-3) 1.755 Reflections collected 7239 Independent reflections 2146 Rint 0.0203 Data/restraints/parameters 2146/39/223 Goodness-of-fit on F 1.084 0.0315 Final R [I > 2s (I)], R1a wR2b 0.0843 Absolute structure -parameter a R1 = S||Fo| - |Fc||/S|Fo|. b wR2 = [Sw(Fo2 - Fc2)2/Sw(Fo2)2]1/2 IV-2 C9H13ClCuN2O7 360.20 223(2) Monoclinic P21/c 12.2902(9) 7.7560(6) 14.4409(10) 109.410(2) 1298.31(16) 1.921 1.843 7539 2417 0.0254 2417/61/223 1.057 0.0363 0.0896 -- IV-3 C8H11ClCuN2O8S 394.24 223(2) Monoclinic C2/c 24.4452(13) 9.0530(5) 13.0236(7) 111.5390(10) 2680.9(3) 2.026 1.954 9173 3068 0.0309 3068/0/224 1.048 0.0300 0.0776 -- IV-5a C11H20ClCuN3O9S 469.35 223(2) Monoclinic P21/n 13.2480(17) 6.6691(9) 20.339(3) 96.461(3) 1785.6(4) 1.541 1.746 12036 4103 0.0405 4103/3/246 1.055 0.0473 0.1170 -- IV-6 C16H30CuN4O10S2 566.10 223(2) Monoclinic P21/c 9.1490(3) 11.5270(4) 11.1631(4) 105.4750(10) 1134.59(7) 1.208 1.657 7883 2590 0.0293 2590/4/163 1.177 0.0461 0.1278 -- IV-8 C11H14CuN2O5 317.78 223(2) Orthorhombic P212121 4.9362(3) 10.3712(7) 24.1681(16) 90 1237.27(14) 1.784 1.706 8712 2843 0.0404 2843/0/178 1.057 0.0383 0.0842 0.046(17) 236 Appendix A3. Copyrights Permission I sincerely acknowledge the publishers of American Chemical Society (ACS), WileyVCH Verlag GmbH & Co KG, Royal Society of Chemistry (RSC) and Elsevier B. V (ScienceDirect) for granting copyrights permission to reproduce the figures from the respective journals as below. Permission has been granted for using the following list of figures from various journals of the above mentioned publishers. Copyright permission details are provided as a soft copy in the CD-ROM attached with this thesis. Copyrights permission from American Chemical Society Figure 1-5. Reprinted with permission from Cryst.Growth Des. 2005, 5, 41. Copyright 2005 American Chemical Society. Figure 1-6. Reprinted with permission from Cryst.Growth Des. 2004, 4, 781. Copyright 2004 American Chemical Society. Figure 1-10. Reprinted with permission from Inorg. Chem. 2003, 42, 5135. Copyright 2003 American Chemical Society. Figure 1-13. Reprinted with permission from J. Am. Chem. Soc. 2006, 128, 11663. Copyright 2006 American Chemical Society. Copyrights permission from Wiley-VCH Verlag GmbH & Co KG Figure 1-1. Figure 1-3. Figure 1-7. Angew. Chem. Int. Ed. 1995, 34, 2311. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission. Angew. Chem. Int. Ed. 2003, 42, 1940. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission. Angew. Chem. Int. Ed. 2004, 43, 5769. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission. Copyrights permission from Royal Society of Chemistry Figure 1-2. Dalton Trans. 2000, 3885. (Reproduced by permission of The Society of Chemistry) Figure 1-12. Chem. Soc. Rev. 2005, 34, 821. (Reproduced by permission of The Society of Chemistry) Figure 1-14. Chem. Commun. 2005, 4149. (Reproduced by permission of The Society of Chemistry) Figure 1-15. Chem. Commun. 2008, 6170. (Reproduced by permission of The Society of Chemistry) Royal Royal Royal Royal Copyrights permission from Elsevier B.V. (ScienceDirect) Figure 1-9. Reprinted from Coord. Chem. Rev. 2008, 252, 1027, Copyright (2008), with permission from Elsevier. 237 Appendix A4. Typical spectroscopic data of compounds Complex IIB-2 has been selected as a representative compound in Chapter 2. The IR, UV-vis, TGA and ESI-MS figures are shown below. The characterization details of other complexes can be found in Section 2-A/B-2-3 to 2-A/B-2-5. IR spectra of IIB-2. (a) (b) UV-vis spectra of IIB-2 (a) methanol solution (b) solid state. 238 Appendix TGA of IIB-2. ESI-MS of IIB-2. 239 Appendix Complex IIIA-10 has been selected as a representative compound in Chapter 3. The IR, TGA, ESI-MS and NMR figures are shown below. The characterization details of other complexes can be found in Section 3-A-2-3 to 3-A-2-6 and Part D. IR spectra of IIIA-10. TGA of IIIA-10. 240 8.8 8.4 8.0 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 .1 6 .2 .7 .7 .0 .0 .0 0 In te g r a l .2 .1 .3 .5 0 .8 .8 .9 9 .9 6 .8 .5 .3 .3 Appendix ESI-MS of IIIA-10. 1H normal range AC300 WL099d d6-DMSO (ppm) 2.0 1.6 1.2 0.8 0.4 H NMR spectra of IIIA-10. 241 Appendix 180 150 140 130 120 110 100 90 80 70 60 .2 7 .9 .9 .4 5 .8 1 .4 1 .4 160 .7 170 .1 5 .4 .9 190 .5 .4 13C Standard AC300 WL099d d6-DMSO 50 40 30 20 10 (ppm) 13 C NMR spectra of IIIA-10. Complex IV-2 has been selected as a representative compound in Chapter 4. The IR, UVvis, TGA and ESI-MS figures are shown below. The characterization details of other complexes can be found in Section 4-2-3 to 4-2-5. IR spectra of IV-2. 242 Appendix (a) (b) UV-vis spectra of IIB-2 (a) methanol solution (b) solid state. TGA of IV-2. ESI-MS of IV-2. 243 Appendix A5. Curriculum vitae Leong Wei Lee Department of Chemistry, Science Drive 3, National University of Singapore, Singapore 117543. Email: weileeleong@nus.edu.sg Education Jan 2005 – Aug 2009 National University of Singapore, Singapore, Ph.D in Supramolecular Chemistry Title of thesis: Metal Complexes of N-(7-hydroxy-4-methyl-8-coumarinyl)-amino acid, N-(2-pyridylmethyl)-amino acid and Related Ligands: Synthesis, Structural, Photophysical and Gelation Properties. Jun 2000 – Mar 2004 Universiti Teknologi Malaysia, Malaysia. B. Sc. (Chemistry Hons.) Title of thesis: Speciation of Selenium Species Using Voltammetry Techniques. Scholarship and Awards 1. The National University of Singapore Research Scholarship (2005~2009). 2. Part-time Teaching Assistant Award 2006/2007, National University of Singapore. 3. Dean Appreciation Certificate, University Technology of Malaysia, Malaysia. Research Interests 1. Crystal engineering: Rational design of metal coordination polymers with multidimensional network structures using reduced Schiff base of amino acid derivatives. Study on supramolecular interactions of molecules in order to understand the supramolecular nature of molecules that influence the crystal packing and functional properties. 2. Gelation of coordination polymer: Fabrication of coordination polymer into hydrogel and fiber materials and study the photophysical, morphological and rheological properties of hydrogels. 244 Appendix Publications 1. Rugayah Mohamed, Leong Wei Lee, Analysis of Selenium Species Using Cathodic Stripping Voltammetry, Jurnal Teknologi, 2006, 44C, 55-66. 2. Wei Lee Leong, Jagadese J. Vittal, Self-Assembly of Ion-Pair Complexes, Crystal Growth and Design, 2007, 7(10), 2112-2116. 3. Wei Lee Leong, Anthony Yiu-Yan Tam, Sudip K. Batabyal, Lee Wah Koh, Stefan Kasapis, Vivian Wing-Wah Yam and Jagadese J. Vittal, Fluorescence Enhancement of Coordination Polymeric Gel, Chemical Communications, 2008(31), 3628-3630. (Inside coverpage) 4. Wei Lee Leong, Sudip K. Batabyal, Stefan Kasapis, Jagadese J. Vittal, Fluorescent Magnesium(II) Coordination Polymeric Hydrogel, Chemistry – A European Journal, 2008, 14(29), 8822-8829. (Coverpage) 5. Wei Lee Leong, Jagadese J. Vittal, Synthesis and Characterization of Metal Complexes of Calcein Blue: Formation of Monomeric, Ion Pair and Coordination Polymeric Structures, Inorganica Chimica Acta, 2009, 362(7), 2189-2199. 6. Sudip K. Batabyal, Wei Lee Leong, Jagadese J. Vittal, Fluorescent Coordination Polymeric Gel from Tartaric Acid Assisted Self-Assembly, submitted. 7. Mangayarkarasi Nagarathinam, Saravanan Kuppan, Wei Lee Leong, Palani Balaya, Jagadese J Vittal, Hollow Nanospheres and Flowers of CuS from Self-Assembled Cu(II) Coordination Polymer and Hydrogen-bonded Complexes of N-(2-hydroxybenzyl)-Lserine, submitted. 8. Wei Lee Leong, Sudip K. Batabyal, Stefan Kasapis, J. J. Vittal, Chirality and pH Dependent Mesoscale Assembled Structure of Coordination Polymer into Aligned Fiber, submitted. Conference presentation 1. Dec 2005 Singapore International Chemical Conference (SICC), Singapore, poster presentation. 2. Dec 2006 Mathematics and Physical Science Graduate Conference (MPSGC), Singapore, poster presentation. 3. Dec 2006 International Symposium for Chinese Inorganic Chemists (ISCIC), Singapore, poster presentation. 4. Dec 2007 MPSGC, Malaysia, poster presentation. 5. Feb 2008 MRS-S Conference on Advanced Materials (MPS-S), Singapore, poster presentation. 6. Apr 2008 American Chemical Society National Meeting, New Orleans, USA, oral presentation. 7. Dec 2008 MPSGC, Singapore, oral presentation. 245 [...]... In this study, three different types of multidentate amino acid ligands have been employed to investigate their coordination behavior with divalent transition and main group metal ions They are 4- methylumbelliferone -8- methyleneiminodiacetic acid (H3muia), N- (7- hydroxy -4- methyl- 8- coumarinyl)- amino acid (amino acid = glycine (H2mugly), alanine (H2muala), serine (H3muser)) and N- (2- pyridylmethyl) -amino. .. engineering can be defined as the understanding of intermolecular interactions in the context of crystal packing and in the utilization of such understanding in the design of new solids with desired physical and chemical properties. 5 The aim of crystal engineering is to establish reliable connections between molecular and supramolecular structures on the basis of intermolecular interactions The synergistic... European Journal, 20 08, 14( 29), 88 22 -88 29 (Coverpage) 4 Wei Lee Leong, Jagadese J Vittal, Synthesis and Characterization of Metal Complexes of Calcein Blue: Formation of Monomeric, Ion Pair and Coordination Polymeric Structures, Inorganica Chimica Acta, 2009, 36 2(7) , 2 189 -2199 Conference presentation 1 Poster presentation at Singapore International Chemical Conference (SICC -4, 8- 10 Dec 2005), Singapore... with p-p interactions in the solid-state structures Driven by these results, the coordination chemistry of coumarin derivatized amino acid ligands is further explored in Chapter 3 In Part A, the synthesis and characterization of Cu(II), Ni(II), Zn(II), Mg(II) and Ca(II) complexes of N- (7- hydroxy4 -methyl- 8- coumarinyl)- amino acid have been described Interestingly, variation the metal ions and solvents have... (c) confocal laser scanning image Schematic representation of the self-assembly process of the CP gels Structure of Calcein Blue ligand Coumarin derivatized amino acid, N- (7- hydroxy -4- methyl- 8coumarinyl)- amino acid ligand structures N- (2- pyridylmethyl) -amino acid ligands Chapter 2 A perspective view of IIA-1 showing the (H2O)3 cluster A portion of the 2D structure present in the crystal structure of IIA-1... Hydrogen bond lengths (Å) and angles (°) for III-b Hydrogen bond lengths (Å) and angles (°) for IIIA-2 Hydrogen bond lengths (Å) and angles (°) for IIIA-7 Hydrogen bond lengths (Å) and angles (°) for IIIA -8 Hydrogen bond lengths (Å) and angles (°) for IIIA-10 Hydrogen bond lengths (Å) and angles (°) for IIIA-11 Selected IR absorption bands (cm-1) in IIIA-1 to IIIA-17 Solution and solid state fluorescence... chain appended groups, coordination polymers have been demonstrated to be able to achieve gelation Coordination polymeric gels have provided new insight of properties, functionality and application compared to their highly crystalline counterpart In Chapter 4, the synthesis and characterization of Cu(II) complexes of N- ( 2pyridylmethyl) -amino acid ligands have been discussed The role of carboxylate and. .. Table 2- 14 Table 2-15 Chapter 2 Hydrogen bond distances (Å) and angles (°) for IIA-1 Hydrogen bond distances (Å) and angles (°) for IIA-2 Hydrogen bond distances (Å) and angles (°) for IIA-3 and IIA -4 Hydrogen bond distances (Å) and angles (°) for IIA-5 Hydrogen bond distances (Å) and angles (°) for IIA-6 Selected IR absorption bands (cm-1) in IIA-1 to IIA -8 UV-vis data of IIA-1 to IIA -8 TG data of IIA-1... sulfonate functional group in Cu(II) coordination have been evaluated based on Schiff base and its reduced form with b-alanine and amino ethane sulfonic acid Furthermore, reduced Schiff base ligands with additional functional groups in the amino acid side chain, namely L-serine and L-glutamic acid have been utilized in the complexation with Cu(II) These Cu(II) complexes have been demonstrated as one-dimensional... O Me N H OH2 O Ca O H2 O O XVII IIIA-16 O [Ca(muala)(H2O)2]·0.5H2O O Me Me N H O Ca O OH2 Ca O Ca O H2 O O IIIA-17 O [Ca(Hmuser)(H2O)2] O OH Me N H OH2 Ca O O H2 O O HPbals N- (2- pyridylmethylene)-balanine O N OH N HPbal N- (2- pyridylmethyl)- b -alanine O N H OH N HPaes O N- (2- pyridylmethylene) -amino ethane sulfonic acid O S N OH N HPae O N- (2- pyridylmethyl) -amino ethane sulfonic acid O S N H OH N H2Pser . METAL COMPLEXES OF N- (7- HYDROXY -4- METHYL- 8- COUMARINYL)- AMINO ACID, N- (2- PYRIDYLMETHYL)- AMINO ACID AND RELATED LIGANDS: SYNTHESIS, STRUCTURAL, PHOTOPHYSICAL AND GELATION PROPERTIES. N- (2- pyridylmethyl)- b -alanine N N H OH O HPaes N- (2- pyridylmethylene) -amino ethane sulfonic acid N N S O O OH HPae N- (2- pyridylmethyl) -amino ethane sulfonic acid N N H S O O OH H 2 Pser N- (2- pyridylmethyl)- L-serine. 4- methylumbelliferone -8- methyleneiminodiacetic acid (H 3 muia), N- (7- hydroxy -4- methyl- 8- coumarinyl)- amino acid (amino acid = glycine (H 2 mugly), alanine (H 2 muala), serine (H 3 muser)) and N- (2- pyridylmethyl)- amino