Self-assembled Transition Metal Coordination Frameworks of ...

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W g _ g mm Summary and conclusion assembly of ZX2 grids as ditopic ligands. The coordination geometries of both thiocarbohydrazone and carbohydrazone derived square grids, complexes [Ni(HL')]4(PF(,)4- ‘/zCH,CH2OH- 2.8H2O (la) and [Zn(HL5)]4(BF4)4- l0H2O (29) respectively, have been explicitly solved by single crystal X-Ray diffraction studies. However Cu(ll) ions are found very reluctant to form molecular square grids with the same set of ligands; but with flexible coordination modes multinuclear chelating complexes were synthesized and characterized. The ligands are found capable of coordinating metal centers in the neutral, monoanionic and dianionic forms subject to reaction conditions. Conversely, Cu(II) carbohydrazone complexes are found not very stable in their solutions of common organic solvents on exposure to air. However, all complexes are found very stable in the solid state. As expected, the Mn(II) complexes were also found labile in their solutions in organic solvents, especially at lower concentrations. Hitherto reported complexes of carbohydrazones were all mononuclear or dinuclear in nature. However our study is observed first time for carbohydrazone derivatives behaving as the building blocks for self-assembly, and thereby offers a new dimension to metallosupramolecular squares. The novel N40 coordination, with bridging mode of the carbonyl group, offers carbohydrazone ligands as a building block for interesting frameworks through self-assembly. The two-dimensional molecular square grids are precise and easy to prepare and provide best opportunities to enter the fascinating world of supramolecular chemistry. The carbohydrazide inner core thus offers a wide range of possibilities with suitable substituents having different coordination properties to build novel coordinating ligands for designing multinuclear coordination complex frameworks of desired metals, which would find applications in various fields. The materials with uncoordinated ligand donor atoms after assembly possess chemically active sites and are expected to be useful for homogeneous or heterogeneous catalysis, or as molecular sensors. These kinds of complexes shall
g g 7 g Self-Assembled Transition Metal Coordination further be used as a substrate for further complexation or to design mixed-metal complexes. The complexes reported here possess uncoordinated donor atoms and this is better in complexes derived from di-2-pyridyl ketone derived ligands. Accidentally and fortunately complex la, got crystallized from a solution of complex 1, is found to have two trapped water molecules inside the four uncoordinated pyridyl groups. This kind of water of crystallization as a receptee and associated hydrogen bonds are supramolecularly very potent. The pyridyl group, selected here, is a very vital substituent in the light of various biological activities shown by thiosemicarbazone and other related potential compounds possessing it. Similarly, quinoline group, an equivalent analogue thereof, also has a unique position in drug chemistry. So we found it worthwhile to go for an immediate direction towards pharmaceutical applications. Also there was anticipation of anticancer drug analogues for thiocarbohydrazones. In the light of these aspects we carried out preliminary anticancer studies of selected compounds and included in the thesis. The chapter wise conclusions of the thesis are as described below. Chapter 1 depicts a brief survey of the previous research works in the field of carbohydrazones and thiocarbohydrazones, their applications, importance of multinuclear coordination compounds, method of self-assembly and metallosupramolecular squares. The thiocarbohydrazone ligands possessing mainly two binding units, unlike thiosemicarbazones, are found to have the possibility of forming multinuclear compounds and for behaving as building blocks for self assembly to form molecular square grids. The different analytical and spectroscopic techniques used for the analysis of the ligands and metal complexes are also discussed. Chapter 2 includes syntheses of carbohydrazone, thiocarbohydrazone and thiosemicarbazone ligands and their spectral characterization by elemental analysis, IR, UV-vis and different NMR techniques with a comparative study. X-Ray crystal structures of two new ligands HZL3 and HZL-4 are also reported. All compounds were '2v4_ i_' "_i T
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7,2/H5 Self-assembled Transition Me
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, Phone orr. 0484-2575804 ; Phone R
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‘ilC7(,'NO’WLQ'I(D QEMEWT In tl
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PREFACE In its method, chemistry is
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CONTENTS CHAPTER 1 Introduction to
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4.3.5. Magnetochemistry 4.3.6. Char
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Chapter I__ _ _ irreducible, is a n
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Chapter I W 7 _ W _ 7 pg _ jg to pr
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Chapter I H_ g g 7 g 7 7 __ harvest
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Chapter I _ _ ______g__H _ g involv
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Chapter I _ g plays a pivotal role
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Chapter I g g _ exhibit considerabl
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Chapter I _, assemblies to generate
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Chapter I _ ,_ of mono or dinuclear
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Chapter I M W 7 7 _ __ 1.3.1.1. Ant
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Chapter I _ _ _ _ \_ 4- Jm _. _.
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Chapter In g_ g _ E __ _ E __( > es
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Chapter I W__‘ _ 1.6.6. MALDI MS
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Chapter I ,,_ g electron spin (the
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Chapter I W _ _ Traditional magnets
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Chapter I L.K. Thompson, O. Waldman
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Chapter I i __ _ Org. Chem. 31 (200
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Chapter In _g , g H g 85. S. Padhye
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Chapter 2 1 g anticipation of Cu(H)
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Chapter 2 _. M_ _ up 1. Quinoline-2
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Chapter 2 chloroform solution and d
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Chapter2 V _ _ _ _, 7 _ with aceton
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Chapter 2 _ 7 f __ i 2.3. Results a
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100s0- I > J 20
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— — 1 Ligands 1
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Ligands The ‘H and "C NMR spectra
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Ligands The ‘H NMR spectrum of HZ
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M1 1‘ 11 IL; Fig. 2.11. 'H NMR sp
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' | Ligands uo no 1&0 150 no no no
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Ligands Table 2. 3. Crystal data an
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Ligands The C-S bond distances of 1
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ligands between the planes of Cg(2)
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" F Ligands A indicates a typical d
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' ' Q 0' ¢ ¢" .~ 0~ I Q Q Q \ ' Q
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2.4.2. M TT Cell Proliferation Assa
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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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Page 253 and 254: Chapter 6 The compound 27 exhibits
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Page 259 and 260: Chapter 6 6.3.2. Electronic and IR
Page 261 and 262: Chapter 6 band at 19160 and 23920 c
Page 264 and 265: Zinc(II) & Cadmium(II) complexes Th
Page 266 and 267: .- 60- I ‘J TZinc(Il) & Cadmium(l
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Page 270 and 271: Zinc(II) & C admium(ll) complexes T
Page 272 and 273: Fig. 6.25. The molecular structure
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Page 276 and 277: Zi!lC(II) & Cadmlum(II) C0mlexes Ta
Page 278 and 279: V _ i Zinc(1I) & Cadmium(lI) comple
Page 280 and 281: _ g _ g g V Zinc(lI) & Cadmiumfll)
Page 282 and 283: _, _ g pg L Summary and conclusion
Page 286 and 287: __ ,_ _ W A _ _ Summary and conclus
Page 288 and 289: Curriculum Vitae PERSONAL PROFILE N
Page 290: 2-Hydroxyacetophenone 4-phenylthios
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