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Manganese(II) complexes D and E , etc. The g values other than that at ~2 of 19 and 20 were calculated from the spectra without simulations. For all complexes, EPR spectral simulation was done by considering them as mononuclear Mn(II) systems, i.e. under the investigation conditions. The simulations of 19 (Fig. 5.7) and 20 (Fig. 5.8) are not matching well with mononuclear Mn(H) models, as they doesn’t show g values other than at ~2; however, the simulation at the hyperfine sextet could yield precise values of g and A , though the D -term might be unreliable, due to wrong model usage. However, the simulations of 21 (Fig. 5.9) and 22 (Fig. 5.10) are in well agreement with experimental spectra and suggesting the possible decomposition of these complexes in DMF. All manganese complexes, except 23, exhibit a resonance at g '~“- 2, show a six line hyperfine structure, which is due to the interaction of electron spin of manganese ions with its own nuclear spin [=5/2. The g value for the hyperfine splitting is indicative of the nature of bonding in the matrix. The strength of the hyperfine splitting depends on the matrix into which the ion is dissolved and is mainly determined by the electronegativety of the neighbors. This means a qualitative measure of the covalency of the bonding in the matrix that can be determined from the value of A ; the smaller the splitting, the more covalent the bonding of the anion. In the spectra of all the complexes additional forbidden lines are observed in between each of the two lines of the central hyperfine sextet. These lines are arising by the violation of Am|= :k() of allowed transitions (Am,= il, Am|= :l:0). The EPR spectrum of 19 exhibits a well-defined hyperfine sextet at g =1 .995. Several additional features can be observed including five other ESR resonances at g=7.l6l, g=4.002, g=3.239, g= 2.473 and g=l.582 as small disturbances. A similar, but along with two sets of eleven lines are reported for a dinuclear Mn(H) system in X-band frozen solution spectrum [35]. The hyperfine coupling constant 209
Chapter 5 value of 265 MI-lz (94.9 G) at g=l.995 is consistent with octahedral coordination [36]. The average separation of the forbidden hyperfine lines lying between each of the two main hyperfine lines in the spectrum is approximately 55.8 Ml-lz (20 G). A D value of 460 MHz (1 .5344xl0'2 cm“, 164.74 G) was used for simulation. * i I I I I 20 I20 220 Q0 420 5, h\Tl L___ I _ l_ . . I _ _l_ L . I . ._ _I 280 330 $0 340 $0 $0 430 420 B, WT] Fig. 5.7. The sextet part at g=l.995 of EPR spectrum of 19 (black) and its simulation (blue). The inset shows the full spectrum. The EPR spectrum of 20 also shows some features including a well-defined sextet pattern at g =1.995 . Another g value at 5.074 is also clear in the spectrum. For a dinuclear coupled Mn(II) system an eleven-line hyperfine pattern [2n1+1=4(5/2)+l=l1] with additional features are expected. However, the origin of 210
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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
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
Page 179 and 180: Chapter 4 _|“. / "| 1' '| |' | 1'
Page 181 and 182: Chapter 4 The solid state and some
Page 183 and 184: Chapter 4 U 1 .I - O i I . I II I
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(
Page 212 and 213: Manganese(Il) complexes lcmzmoll in
Page 214 and 215: 1W3 "l U 70 60 40 30 10 490 740 979
Page 216 and 217: Manganese(II) complexes MALDI MS sp
Page 218 and 219: 5.3.2. EPR spectral studies Mangane
Page 222 and 223: the pattern is uncertain and it is
Page 224 and 225: __ I . l r Manganese(II) complexes
Page 226: " |\ Man ganese(II) complexes 80" 6
Page 229 and 230: Chapter 5 thiocarbohydrazone comple
Page 231 and 232: Chapter 5 To fit and interpret the
Page 233 and 234: Chapter 5 #1 IT 0.00 1 — ‘ I '
Page 235 and 236: Chapter 5 The temperature dependenc
Page 237 and 238: Chapter 5 ___ M _ 357 (2004) 2694.
Page 239 and 240: Chapter5 p _ _ S. Sivakumar, Struct
Page 241 and 242: Chapter 6 _ _ __ 7 the latter have
Page 243 and 244: Chapter6A, 0 0 _, 0 0 _* 4, W 0 0 0
Page 245 and 246: Chapter 6 g _ _ [Cd(HL2) ].,(1v0_.)
Page 247 and 248: Chapter 6 / ‘~ ' if‘ . l \ N N/
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
Page 255 and 256: (T71aq7tew'¢5 centered at 1711.9 c
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
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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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