Self-assembled Transition Metal Coordination Frameworks of ...

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__ ,_ _ W A _ _ Summary and conclusion found to exist in their thione tautomeric form in solid state. It is found that the compounds HZLZ and HZLS exhibiting keto-enol tautomerism, while the compound HZLI shows an exclusive presence of its thione tautomer, in their CDC]; solutions. Study of in vitro anticancer activity towards MCF-7 cell lines of selected compounds are also reported, it is seen that the new thiosemicarbazone HL7 shows antiproliferation effect. Chapter 3 describes the synthesis, spectral and structural features of four self assembled molecular square grids of Ni(H) using carbohydrazone and thiocarbohydrazone ligands. Single crystal X-ray diffraction study of one of them is described in details and is in agreement with a molecular square of four Ni(H) octahedral centers, as expected. The MALDI MS spectra are found very useful for the characterization of stable framework complexes. Magneto-structural correlation study shows intramolecular antiferromagnetic coupling between Ni(H) electrons, consistent with the bridging structural arrangement, by a super exchange mechanism through intervening sulfur/oxygen atoms. F our new thiosemicarbazone Ni(Il) complexes were also synthesized and characterized. This include X-ray studies of two mononuclear octahedral Ni(H) compounds. Chapter 4 comprises the syntheses and spectral characterization of twelve copper(ll) complexes using all carbohydrazone and thiocarbohydrazone ligands. Tetranuclear, trinuclear and dinuclear copper(ll) complexes are studied with special emphasis to EPR spectral and variable temperature magnetic properties. However, the Cu(II) compounds, especially from carbohydrazone-derived, are found not very stable in solution or under ionization conditions of MALDI. The lability in solutions is also clear because all the complexes showing antiferromagnetism in the solid state do not exhibit the coupling of electrons in their frozen DMF solution EPR spectra. The EPR parameters, under investigation conditions, were obtained by making use of simulations. In addition, selected compounds were screened for in vitro anticancer activity towards MCF-7 cell lines and the results clearly points to the fact that ligands
A Self-Assembled Transition Metal Coordination showed cell proliferation and their complexation leads to antiproliferation effect. Three complexes are reported as anticancer gadgets against breast cancer. Chapter 5 explains the synthesis and spectral characterization of five Mn(lI) complexes. Variable temperature magnetization study reveals strong antiferromagnetism. Frozen DMF solution EPR spectral studies suggesting possible fragmentations to monomeric species, under investigation conditions, as evidenced by EPR parameters obtained by making use of simulations. MALDI MS spectra reveal lower stability of Mn(lI) complexes in their solutions or under MALDI ionization conditions, but show sensible fragmentation peaks. Magnetic data of four Mn(II) complexes were rationalized successfully on the basis of expected square grid structures in the solid state, as supported by mass and other studies, and is in agreement. Chapter 6 deals the syntheses and characterization of six Zn(II) and two Cd(lI) complexes. All complexes, except two Zn( ll) compounds, exist as molecular square grids and their structural and spectral features are described in detail. This include single crystal X-ray diffraction study of one Zn(ll) molecular square grid derived from a carbohydrazone ligand, H2L5. The results clearly indicate the utility of carbohydrazones as building blocks for self-assembled molecular frameworks. The MALDI MS spectrometry is found an important tool for the explicit characterization, existence and stability of framework complexes in solutions and can be confirmed by theoretical simulations of isotropic distribution pattems of characteristic peaks. Based on the present work we would like to conclude that the carbohydrazones, thiocarbohydrazones and their coordination framework complexes of transition metals are promising systems for wide application in science and technology varied from physics to biotechnology. Novel classes of materials and biologically important potential compounds open up further scope of researches and we hopefully welcome any sort of related research to make this work more valuable. *>ll
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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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Chapter 5 #1 IT 0.00 1 — ‘ I '
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Page 245 and 246: Chapter 6 g _ _ [Cd(HL2) ].,(1v0_.)
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Page 249 and 250: 1 | Chapter 6 100m__ ‘ 76$ mi, 16
Page 251 and 252: 3 - i El Q I Chapter 6 - '3“ 1999
Page 253 and 254: Chapter 6 The compound 27 exhibits
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Page 257 and 258: 1 . 1 Chapter 6 1244 100--1-; 1245
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
Page 268 and 269: Zinc(Il) & Cadmium(Il) complexes re
Page 270 and 271: Zinc(II) & C admium(ll) complexes T
Page 272 and 273: Fig. 6.25. The molecular structure
Page 274 and 275: Zinc(lI) & Cadmium(ll) complexes Al
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 284 and 285: W g _ g mm Summary and conclusion a
Page 288 and 289: Curriculum Vitae PERSONAL PROFILE N
Page 290: 2-Hydroxyacetophenone 4-phenylthios
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