Self-assembled Transition Metal Coordination Frameworks of ...

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DECLARATION I hereby declare that the work presented in this thesis entitled “Self assembled Transition Metal Coordination Frameworks of Carbohydrazone and Thiocarbohydrazone Ligands: Structural, Spectral, Magnetic and Anticancer Properties” is entirely original and was carried out independently under the supervision of Professor M.R. Prathapachandra Kurup, Department oi Applied Chemistry, Cochin University of Science and Technology and has not been included in any other thesis submitted previously for the award of any other degree. 18-l 0-07 Kochi-22 Manoj E. \ (
‘ilC7(,'NO’WLQ'I(D QEMEWT In tliis place, I eaqpress sincere tfianfi to my supervising guide (Prof WLR, Wratfiapacliandra Kurup, ®epartment of/ilpplied Cfiemistry, for providing guidance, freedom and mad: it possifile for me to carry out researcfi. 9{e lias always 5een tfiere to lielp me witli inspirations. I am greatly inifizlited to q)r. ‘IQK Mofiammed (Yusuflfi (Profizssor of Catalysis, (Department qf,’4ppliedCliemzstry, for fiis valualile suggestions, comments and liindliearted fielp as my doctoral committee mem6er. I am gratefid to (Dr. Qirisli Kumar, Head, (Department ofjlpplied Cliemistry, for all liis support. My sincere tlianfis to Qrof S. Sugunan, Tormer Head, (Department offlpplied (fliemistry, for providing necessary lielp. I eagtend my gratitude to (Dr. S. @ratIiapan and G.')r. Q’. /1. Unnzfirisfinan, ®epartment qfflpplied Cliemistry, for necessary fielp and suggestions. I am also tfianliful for tlie support I received from all tlie otlier teacliing and non teacfiing staffqftfie (Dept. of]lpplied(,‘/iemistry, C’US/(IT I wouul like very mucfi to tlianI{_ (Dr. jl. Sreefiantli, Lecturer, (Department of Cliemistry, WM, Tricfii, for His love, lielp and valuafile suggestions tfirougliout my researcfi wor/Q6): various means and for ma§ing my life in C’US/WT valua6&. He lias always 5een witli me, wlienever I needed Help. I am greatly indelited to fiim for €E(PK and 914/’4L(DI MS measurements also. I deeply acénowledge tlie Kerala State Council for Science ‘Iecfinology QZ ‘Environment, ‘Iliiruvanantliapuram, and tlie ‘University §rants Commission, New (Dellii, for financial support in tlie form offizllowsfiip. I sincerely tlianfi (Dr. HI-‘K. Tun, X-ray Crystallograpliy Unit, Scliool of Q°liysics, ’Universiti Sains 9|/fafizysia, Q’enang, 5"1'(aQ1ysia, (Dr. 914. Wetfiaji, (Department of Inorganic and (Pliysical Cliemistry, IISc, Qangalore, and (Dr. Q1 Suresfi, CSMCRI, Qujarat, for singé crystal X-ray diffraction studies. I am tlianfiful to (Dr. jlleag Q°unnoose, (Department of @liysics, Qoise State ‘University, Q3oise, IQ) 83 725-1 5 70, U. S. /(1., for magnetic data measurements. I eagtend my tlianfis to tlie fiead of tfie institutions ofS/Q11‘? Kocfii, II(I'Q3om6ay and II‘T Roorfiee for tlie services rendered in sample analyses.
Page 1 and 2: 7,2/H5 Self-assembled Transition Me
Page 3: , Phone orr. 0484-2575804 ; Phone R
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 and 32: Chapter I _ _ _ _ \_ 4- Jm _. _.
Page 33 and 34: Chapter In g_ g _ E __ _ E __( > es
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
Page 58 and 59:
100s0- I > J 20
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
Page 78 and 79:
' ' Q 0' ¢ ¢" .~ 0~ I Q Q Q \ ' Q
Page 80 and 81:
2.4.2. M TT Cell Proliferation Assa
Page 82 and 83:
Table 2.9. Cell proliferation effec
Page 84 and 85:
7 y _ i _ W Ligands B. Moubaraki, K
Page 86 and 87:
CHAPTER Ni(II) complexes of carbohy
Page 88 and 89:
_ _ __ g_ g W g H__ Ni(ll) complexe
Page 90 and 91:
_ g A __ Ni(lI) complexes The reddi
Page 92 and 93:
3.3. Results and discussion g_g _ N
Page 94 and 95:
3.3.1. MALDI MS spectral studies of
Page 96 and 97:
Ni(Il) complexes In the case of com
Page 98 and 99:
100 U-
Page 100:
3.3.2. IR and electronic spectral s
Page 103 and 104:
Chapter 3 The electronic spectra of
Page 105 and 106:
t§hqphw*3 v(Ni—S), further suppo
Page 107 and 108:
Chapter 3 charge transfer bands. Fo
Page 109 and 110:
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
Page 132 and 133:
11 12 13 14 15 16 17 18 19 20 21 22
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 162 and 163:
2 5 2.5MW 20 Q 1.51 2oo'aoo'45o's
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
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 220 and 221:
Manganese(II) complexes D and E , e
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
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 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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