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2 5 2.5MW 20 Q 1.51 2oo'aoo'45o'soo'eoo'1oo'aoo'ai>o C0pper(Il) complexes I I I I I I I I I I wavelength (nm) Wavelength (nm) I I 300 400 500 000 700 000 000 Fig. 4.19. Electronic spectra of Cu(lI) carbohydrazone complexes 14 in 104 M DMSO (left) 15 in 10* M DMF (right) 2.5 2.0 I ' I ' I ' I 3°°‘°°5°°°°°7°°°°°°°° aoo'4oo'seo'eoo1ooaooeoo Wavelength (nm) WWQIQHQIII (nm) Fig. 4.20. Electronic spectra of Cu(II) carbohydrazone complexes 16 (left) and l7 in 10*‘ M DMF (right). 2.0 15 0.0 25 20 0.0 3°°‘°°5°°°°°7°°'°°°°° aoo-soosooeoorooaooeoo I I I I I I I wav°'°"9m (nm) Wavelength (nm) Fig. 4.21. Electronic spectra of Cu(ll) carbohydrazone complexes 18 (left) and 19 in 10" M DMF (right). 25 20 151
Chapter 4 4.3.4. EPR spectral studies The EPR spectra of all the complexes in frozen DMF solutions at 77 K were recorded in the X-band using a cw EPR spectrometer. All compounds under the investigation condition exhibit signals characteristics of uncoupled Cu(H) species at ~3300 G and not showed signals typical for coupled binuclear complexes. The binuclear complex is connected with the antiferromagnetic coupling of two Cu(H) ions, leading to a singlet ground state and an excited spin triplet state. For a coupled system of two Cu(H) species equally distributed seven hyperfine features (2nI+l; n=2 and I=3/2) are expected. However none of the frozen solution spectra show this feature and half field signals, and the computer simulation of most of the compounds is in good agreement with the presence of two uncoupled Cu(H) species. This frozen DMF features are in contradiction with the solid-state magnetic studies, is attributed to the possible fragmentation in DMF at low concentrations. Absence of any half-field signals in solution for all the compounds may be due to the absence of any considerable Cu—Cu interactions, and might be due to the absence of enough intensity. Another possibility is the dissociation of dinuclear to mononuclear copper compounds and presence of an equilibrium mixture with greater monomer percentage. The EPR spectra of binuclear compounds are reported to dissociate to yield a series of mononuclear species, depending upon concentration [29]. The copper (II) ion, with a 3 d 9 configuration, has an effective spin of S = ‘/2 and is associated with a spin angular momentum, ms = :l:l/2, leading to a doubly degenerate spin state in the absence of a magnetic field. In a magnetic field the degeneracy is lifted between these states and the energy difference between them is given by E = h v = g,3B , where h is Planck’s constant, v is the frequency, g is the Lande splitting factor (equal to 2.0023 for a free electron), ,5 is the Bohr magneton and B is the magnetic field. The appropriate axially symmetric spin Hamiltonian [30,31] is then given by, 152
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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
Page 111 and 112: Chapter 3 3.3.3.1. Crystal structur
Page 113 and 114: Chapter 3 Table 3.7. Selected bond
Page 115 and 116: Chapter 3 N(l3)—C(35), N(2l)-C(58
Page 118 and 119: 3.3.3.2. Crystal structures 0f[Ni(H
Page 120 and 121: Table 3.10. Selected bond lengths (
Page 122 and 123: Ni(lI) complexes significant 1t---1
Page 124 and 125: 3.3.4. Magnetochemistry of the mole
Page 126 and 127: Ni(Il) complexes The allowed values
Page 128 and 129: in xn In
Page 130 and 131: g 7 Ni(Il) complexes 3.4. Concludin
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Page 134 and 135: 41 42 43 44 45 46 47 48 49 50 51 52
Page 136 and 137: _ g “FOUR CHAPTER Cu(II) complexe
Page 138 and 139: _g C0pper(II) complexes complex of
Page 140 and 141: _ _ , p f 7, Copper-(II) complexes
Page 142 and 143: pp g _g _4_,_ C0pper(II) complexes
Page 144 and 145: g _,_,_ g g Copperfll) complexes in
Page 146 and 147: i ____ 3+ i --—- C 0pper(H) 2+ co
Page 148 and 149: C0pper(Il) complexes 499 100i ~04 7
Page 150 and 151: .04Copper(II) complexes 385 50.1I 1
Page 152 and 153: 100-I 4 -1 U ” Q 7°-J 59-: "1
Page 154: C0pper(lI) complexes confirm the po
Page 158 and 159: C0pper(ll) complexes 100 80" I
Page 160 and 161: C0pper(1l) complexes state, similar
Page 164: Copper(lI) complexes F1 = g",3B:S:
Page 167 and 168: Chapter 4 for both species consider
Page 169 and 170: Chapter 4 The spectrum of compound
Page 171 and 172: Chapter 4 stability alone could not
Page 173 and 174: Chapter 4 zénzénzénzénénaloeé
Page 175 and 176: Chapter 4 164 | | | 252 272 2Q 31 B
Page 177 and 178: Chapter 4 The shifting of g values
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Page 181 and 182: Chapter 4 The solid state and some
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Page 185 and 186: _ I Chapter 4 — I I I — I '
Page 187 and 188: . , Chapter 4 2.5 I I ' I ' I ' I '
Page 189 and 190: Chapter 4 The field dependence of m
Page 191 and 192: Chapter 4 Where ,1’ M is the magn
Page 193 and 194: Chapter 4 g e The powder and frozen
Page 195: Chapter 4 various aspects like bond
Page 198 and 199: C0pper(ll) complexes Table 4.6. Sel
Page 200 and 201: ,____ p _p C0pper(H) complexes from
Page 202 and 203: Ed. Engl. 31 (1992) 733. 7___7 7 7
Page 204 and 205: __ ,_ f W C 0pper(l1) complexes Che
Page 206 and 207: -_ FIVE CHAPTER Spectral and magnet
Page 208 and 209: __ g_ _g g H g __ Manganese(II) com
Page 210 and 211: 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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