Self-assembled Transition Metal Coordination Frameworks of ...

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W 7 N A _ gm g_ g Manganesefll) complexes reported for the first time. The MALDI MS spectra reveal sensible fragmentation peaks of tetranuclear molecular squares, and it is found that the Mn(II) squares are not so stable like their Ni(Il) counterparts in solution or under ionization conditions of MALDI. The Mn(II) complexes were organized by mono and dideprotonated thiocarbohydrazones and by monodeprotonated and neutral carbohydrazones. Variable temperature magnetic studies of all the Mn(ll) square grids exhibit intramolecular antiferromagnetic coupling between electrons, consistent with the expected bridging structural arrangement, by a super exchange mechanism through intervening sulfur/oxygen atoms. Magnetic data have been rationalized successfully on the basis of expected square grid structures, as supported by MALDI MS and other data, in the absence of single crystal X-ray studies. The theoretical simulations of isotropic patterns of characteristic fragmentation peaks were achieved well, confirm the proposed structural formulae and this is found inevitable in the absence of single crystal X-ray studies. The molar conductance, magnetic studies and elemental analyses along with other spectral studies differentiate the square grid frameworks from mononuclear metal complexes. However, the complex 20 was found to be a dimanganese(ll) complex, may be due to the effect of concentration or the preference of azide ion to coordinate to metal center. The magnetic complexes, especially the colorless materials derived from carbohydrazones would find applications. References l. N.N. Greenwood, A. Eamshaw, Chemistry of the Elements, 2'“ ed., Reed Educational and Professional, Oxford (1997). 2. T.G. Carrel], A.M. Tyryshkin, G.C. Dismukes, J. Biol. lnorg. Chem. 7 (2002) 2. 3. J.-Z. Wu, E. Bouwman, A.M. Mills, A.L. Spek, J. Reedijk, lnorg. Chim. Acta 225
Chapter 5 ___ M _ 357 (2004) 2694. O. Khan, Molecular Magnetism, Wiley-VCH, New York (1993). R. Sessoli, H.-L. Tsai, A.R. Schake, S. Wang, J.B. Vincent, K. Folting, D. Gatteschi, G. Christou, D.N. Hendrickson, J. Am. Chem. Soc. 115 (1993) 1804. J .-P. Sauvage, C. Dietrich-Buchecker, Molecular Catenanes, Rotaxanes and Knots Wiley-VCH, New York (1999). J. Nugent, Ed. Photosynthetic water oxidation. Biochim. Biophys. Acta. Bioenerg. Special dedicated issue. 1503 (2001) 1. K.N. Ferreira, T.M. lverson, K. Maghlaoui, J . Barber, S. Iwata, Science 303 (2004) 1831. T. Glowiak, H. Kozlowski, L.S. Enre, G. Micera, Inorg. Chim. Acta 236 (1995) 149. M.B. Ferrari, G.G. Fava, C. Pelizzi, P. Tarasconi, G. Tori, J. Chem. Soc., Dalton Trans. (1987) 227. B.S. Garg, M.R.P. Kurup, S.K. Jain, Y.K. Bhoon, Trans. Met. Chem. 13 (1988) 92. P. Bindu, M.R.P. Kump, J.I. Bhat, J. Electrochem. Soc. Ind. 48 (1999) 154. R.P. John, A. Sreekanth, H.-K. Fun, M.R.P. Kurup, Polyhedron 24 (2005) 601. A. Usman, I.A. Razak, S. Chantrapromma, H.-K. Fun, A. Sreekanth, S. Sivakumar, M.R.P. Kurup, Acta. Cryst. C 58 (2002) m46l. H.A. Tang, L.F. Wang, R.D. Yang, Trans. Met. Chem. 28 (2003) 395. V. Philip, V. Suni, M.R.P. Kurup, M. Nethaji, Spectrochim. Acta Part A 64 (2006) 171. M.-L. Tong, S.-L. Zheng, J.-X. Shi, Y.-X. Tong, H.K. Lee, X.-M. Chen, J. Chem. Soc., Dalton Trans. (2002) 1727.
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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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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
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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: Chapter 5 The temperature dependenc
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Page 241 and 242: Chapter 6 _ _ __ 7 the latter have
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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
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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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