Self-assembled Transition Metal Coordination Frameworks of ...

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__ A A A __AA_*_Ag Zinc(Il) & Cadmium(II) complexes H2L2 in absolute ethanol coordination is found to occur through monodeprotonated form. Ali et al. [l4] have reported the formation of a neutral Cd(II) complex (by dideprotonated form of ligand) under the same condition and remarked the importance of nitrate anion over chloride in ethanol for consuming protons released upon complexation. The conductance measurements in DMF showed all the complexes except 24 and 26, are electrolytes of 1:4 or higher ratio. The molar conductance study is found an important tool for assigning the formation of multinuclear complexes. The conductance values of 24 and 26, as 12 and 20 Q'lcm2mol'l in lO'3 M DMF solutions respectively, are suggestive of non-electrolytic nature for these compounds [31]. However, all the other complexes show conductivity in lO'4 M DMF solutions as 40, 36 and 26 Qlcmzmoll for 25, 27 and 29 respectively. The two thiocarbohydrazone Cd(II) complexes 30 and 31 show conductance values of 87 and 40 Q'lcm2mol" in 10' 4 M DMF solution, suggesting the conductance of 30 is almost twice as that of 31. The proposed molecular formulae agree well with these results. All the Zn(Il) complexes and Cd(II) complex 31 prepared are yellow in color. All these complexes, except 28, were found to be soluble in DMF, but only partially soluble in other organic solvents such as DMSO, CHCI3, ethanol, methanol etc. The poor solubility of 28 made it difficult even to measure the conductivity with a known concentration. The Cd(Il) complex 30 is with a red glassy appearance, readily soluble in all common organic solvents. The poor solubility of Zn(II) and Cd(ll) complexes in DMSO-d6 and CDC]; made it difficult to obtain good quality ‘H NMR spectra. Also, the assignments of protons are found difficult in the region 7 - 9 ppm as they are seen as multiplets and with low intensity. Peaks of NH protons are however present in the spectra of some complexes with low intensity, but their absence do not implies the loss of —NH protons especially with poorly low intensity spectra. Tentative structures of all Zn(ll) and Cd(ll) complexes are given in Schemes 6.1 to 6.3. 235
Chapter 6 / ‘~ ' if‘ . l \ N N/\_ N\NH hi \ \ | / \ ’=‘ H/N\ /H S_ Y / 5* / . L H :\ /' = n N/ ...*
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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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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: Chapter 6 g _ _ [Cd(HL2) ].,(1v0_.)
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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