Self-assembled Transition Metal Coordination Frameworks of ...

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Introduction carbohydrazone [65] as it shows amidoketone tautomeric form. However, the enol tautomer (in solution) can adopt a syn or anti configuration as a consequence of the double-bond character of the central N—C linkage. The syn configuration is essential for getting molecular square architectures of thiocarbohydrazone derived octahedral centers. So far reported square complexes [28-31] are all formed with syn configuration of respective ligands in deprotonated forms. 1.5. Objectives of the present work Since the properties of any material are largely due to its structure, control over the structure allows to manipulate these properties. By judicious choice of preferred ligand and metal coordination geometries, control over the topology can be gained. On the other hand, therapeutic applications of inorganic chemistry in medicine are varied, encompassing many aspects of the introduction of metal ions into the body. These successful developments of metallo-pharmaceutical compounds also have prompted many researchers to provide other types of therapeutic agents using the unique and characteristic properties of metal ions. Carbohydrazone and thiocarbohydrazone structures are found to show different specific properties like different potential biological activities, energetic materials (as they are derivatives of energetically important hydrazines), etc and are least studied, in addition to the capability to act as building blocks for metal-organic frameworks. Keeping these in mind we undertook the present work with the following objectives. > design, synthesize and characterize some chelating ligands, carbohydrazones and thiocarbohydrazones, and compare their spectral features > study the coordination behavior of these ligands towards selected metal ions > to use these ligands as building blocks to synthesize novel self-assembled molecular square grid complexes Y’ better understanding of the structural and spectral properties of the complexes 21
Chapter In g_ g _ E __ _ E __( > establishing the structure of the complexes mainly by mass and single crystal X-ray crystallography > to investigate the magnetic characteristics of complexes and possible magnetostnictural correlation study > and to study anticancer properties of selected compounds 1.6. Physico-chemical techniques The characterization of organic ligands and their metal complexes takes advantage of several conventional and modem physico-chemical techniques. A brief account of these methods used in the present study is discussed below. 1.6.1. Elemental analyses and conductivity measurements Elemental analyses of all compounds were carried out using an Elementar Vario EL III CHNS analyzer at SAIF, Kochi, India. The molar conductivities of the metal complexes in organic solutions at room temperature were measured using a direct reading conductivity meter. TG scans in air atmosphere using a Perkin Elmer, Diamond TG/DTA at SAIF, Kochi. 1.6.2. NMR spectra 'H NMR, “C NMR and DCTB13S spectra of compounds in CDCl3 or DMSO-d6 were recorded using Bruker AMX 400/500 FT-NMR spectrometer using TMS as the internal standard at National Chemical Laboratory, Pune, India. The 135° decouple pulse sequence of DCTB produces a carbon spectrum with methyl (CH3) and methyne (CH) carbons are up, but methane (CH2) carbons are down. 1.6.3. Electronic spectra Electronic spectra of organic ligands and their metal complexes (200-900 nm) were recorded on a Varian, Cary 5000 version 1.09 UV-vis spectrophotometer. 22
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Page 7 and 8: PREFACE In its method, chemistry is
Page 9 and 10: CONTENTS CHAPTER 1 Introduction to
Page 11 and 12: 4.3.5. Magnetochemistry 4.3.6. Char
Page 13 and 14: Chapter I__ _ _ irreducible, is a n
Page 15 and 16: Chapter I W 7 _ W _ 7 pg _ jg to pr
Page 17 and 18: Chapter I H_ g g 7 g 7 7 __ harvest
Page 19 and 20: Chapter I _ _ ______g__H _ g involv
Page 21 and 22: Chapter I _ g plays a pivotal role
Page 23 and 24: Chapter I g g _ exhibit considerabl
Page 25 and 26: Chapter I _, assemblies to generate
Page 27 and 28: Chapter I _ ,_ of mono or dinuclear
Page 29 and 30: Chapter I M W 7 7 _ __ 1.3.1.1. Ant
Page 31: Chapter I _ _ _ _ \_ 4- Jm _. _.
Page 35 and 36: Chapter I W__‘ _ 1.6.6. MALDI MS
Page 37 and 38: Chapter I ,,_ g electron spin (the
Page 39 and 40: Chapter I W _ _ Traditional magnets
Page 41 and 42: Chapter I L.K. Thompson, O. Waldman
Page 43 and 44: Chapter I i __ _ Org. Chem. 31 (200
Page 45 and 46: Chapter In _g , g H g 85. S. Padhye
Page 47 and 48: Chapter 2 1 g anticipation of Cu(H)
Page 49 and 50: Chapter 2 _. M_ _ up 1. Quinoline-2
Page 51 and 52: Chapter 2 chloroform solution and d
Page 53 and 54: Chapter2 V _ _ _ _, 7 _ with aceton
Page 55: Chapter 2 _ 7 f __ i 2.3. Results a
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Page 60 and 61: — — 1 Ligands 1
Page 62 and 63: Ligands The ‘H and "C NMR spectra
Page 64 and 65: Ligands The ‘H NMR spectrum of HZ
Page 66 and 67: M1 1‘ 11 IL; Fig. 2.11. 'H NMR sp
Page 68 and 69: ' | Ligands uo no 1&0 150 no no no
Page 70 and 71: Ligands Table 2. 3. Crystal data an
Page 72 and 73: Ligands The C-S bond distances of 1
Page 74 and 75: ligands between the planes of Cg(2)
Page 76 and 77: " F Ligands A indicates a typical d
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Table 2.9. Cell proliferation effec
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7 y _ i _ W Ligands B. Moubaraki, K
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CHAPTER Ni(II) complexes of carbohy
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_ _ __ g_ g W g H__ Ni(ll) complexe
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_ g A __ Ni(lI) complexes The reddi
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3.3. Results and discussion g_g _ N
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3.3.1. MALDI MS spectral studies of
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Ni(Il) complexes In the case of com
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100 U-
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3.3.2. IR and electronic spectral s
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Chapter 3 The electronic spectra of
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t§hqphw*3 v(Ni—S), further suppo
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Chapter 3 charge transfer bands. Fo
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Chapter 3 were refined anisotropica
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Chapter 3 3.3.3.1. Crystal structur
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Chapter 3 Table 3.7. Selected bond
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Chapter 3 N(l3)—C(35), N(2l)-C(58
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3.3.3.2. Crystal structures 0f[Ni(H
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Table 3.10. Selected bond lengths (
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Ni(lI) complexes significant 1t---1
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3.3.4. Magnetochemistry of the mole
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Ni(Il) complexes The allowed values
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in xn In
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g 7 Ni(Il) complexes 3.4. Concludin
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11 12 13 14 15 16 17 18 19 20 21 22
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41 42 43 44 45 46 47 48 49 50 51 52
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_ g “FOUR CHAPTER Cu(II) complexe
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_g C0pper(II) complexes complex of
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_ _ , p f 7, Copper-(II) complexes
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pp g _g _4_,_ C0pper(II) complexes
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g _,_,_ g g Copperfll) complexes in
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i ____ 3+ i --—- C 0pper(H) 2+ co
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C0pper(Il) complexes 499 100i ~04 7
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.04Copper(II) complexes 385 50.1I 1
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100-I 4 -1 U ” Q 7°-J 59-: "1
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C0pper(lI) complexes confirm the po
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C0pper(ll) complexes 100 80" I
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C0pper(1l) complexes state, similar
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2 5 2.5MW 20 Q 1.51 2oo'aoo'45o's
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Copper(lI) complexes F1 = g",3B:S:
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Chapter 4 for both species consider
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Chapter 4 The spectrum of compound
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Chapter 4 stability alone could not
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Chapter 4 zénzénzénzénénaloeé
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Chapter 4 164 | | | 252 272 2Q 31 B
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Chapter 4 The shifting of g values
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Chapter 4 _|“. / "| 1' '| |' | 1'
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Chapter 4 The solid state and some
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Chapter 4 U 1 .I - O i I . I II I
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_ I Chapter 4 — I I I — I '
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. , Chapter 4 2.5 I I ' I ' I ' I '
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Chapter 4 The field dependence of m
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Chapter 4 Where ,1’ M is the magn
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Chapter 4 g e The powder and frozen
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Chapter 4 various aspects like bond
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C0pper(ll) complexes Table 4.6. Sel
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,____ p _p C0pper(H) complexes from
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Ed. Engl. 31 (1992) 733. 7___7 7 7
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__ ,_ f W C 0pper(l1) complexes Che
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-_ FIVE CHAPTER Spectral and magnet
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__ g_ _g g H g __ Manganese(II) com
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q H _ Manganesefll) complexes [Mn2(
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Manganese(Il) complexes lcmzmoll in
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1W3 "l U 70 60 40 30 10 490 740 979
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Manganese(II) complexes MALDI MS sp
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5.3.2. EPR spectral studies Mangane
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Manganese(II) complexes D and E , e
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the pattern is uncertain and it is
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__ I . l r Manganese(II) complexes
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" |\ Man ganese(II) complexes 80" 6
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Chapter 5 thiocarbohydrazone comple
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Chapter 5 To fit and interpret the
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Chapter 5 #1 IT 0.00 1 — ‘ I '
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Chapter 5 The temperature dependenc
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Chapter 5 ___ M _ 357 (2004) 2694.
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Chapter5 p _ _ S. Sivakumar, Struct
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Chapter 6 _ _ __ 7 the latter have
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Chapter6A, 0 0 _, 0 0 _* 4, W 0 0 0
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Chapter 6 g _ _ [Cd(HL2) ].,(1v0_.)
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Chapter 6 / ‘~ ' if‘ . l \ N N/
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1 | Chapter 6 100m__ ‘ 76$ mi, 16
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3 - i El Q I Chapter 6 - '3“ 1999
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Chapter 6 The compound 27 exhibits
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(T71aq7tew'¢5 centered at 1711.9 c
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1 . 1 Chapter 6 1244 100--1-; 1245
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Chapter 6 6.3.2. Electronic and IR
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Chapter 6 band at 19160 and 23920 c
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Zinc(II) & Cadmium(II) complexes Th
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.- 60- I ‘J TZinc(Il) & Cadmium(l
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Zinc(Il) & Cadmium(Il) complexes re
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Zinc(II) & C admium(ll) complexes T
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Fig. 6.25. The molecular structure
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Zinc(lI) & Cadmium(ll) complexes Al
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Zi!lC(II) & Cadmlum(II) C0mlexes Ta
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V _ i Zinc(1I) & Cadmium(lI) comple
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_ g _ g g V Zinc(lI) & Cadmiumfll)
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_, _ g pg L Summary and conclusion
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W g _ g mm Summary and conclusion a
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__ ,_ _ W A _ _ Summary and conclus
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Curriculum Vitae PERSONAL PROFILE N
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2-Hydroxyacetophenone 4-phenylthios
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