Self-assembled Transition Metal Coordination Frameworks of ...

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Ligands The C-S bond distances of 1.6571(2) A in molecule A and 1.6507(3) A in molecule B agree well with those in related compounds [9,3l,32] being intermediate between 1.82 A for a C-S single bond and 1.56 A for a C=S double bond [11]. The C(ll)—N(3) and C(ll)—N(4) bond distances in both molecules are, intermediate between 1.47 A for a C—N single bond and 1.29 A for a C=N double bond [33], indicative of some electron delocalization. Similarly the N(2)—N(3) [l.3545(2) A and 1.3580(2) A in molecules A and B respectively] and N(4)—N(5) [l.3663(2) A and 1.3648(3) A in molecules A and B respectively] bond distances are, intermediate between 1.45 A for a N—N single bond and 1.25 A for a N=N double bond [33], also indicative of extensive electron delocalization in the whole thiocarbohydrazone moiety. The extensive electron delocalization is similar to that seen in bis(2 benzoylpyridine) thiocarbohydrazone [11]. Each molecule is stabilized by three intramolecular hydrogen bonds. The intramolecular N(3)—H(3)---N(1) and N(4)—H(4)---N(6) hydrogen bonds form six membered N(1)—C(9)—C(10)—N(2)—N(3)—H(3) and N(6)—C(13)—C(12)—N(5)—N(4)— H(4) rings respectively in both A and B molecules; while the intramolecular hydrogen bond N(4)—H(4)---N(2) forms a five-membered N(2)—N(3)—C(11)—N(4)—H(4) ring in both A and B molecules (Fig. 2.16 & Table 2.5). The thiocarbohydrazone moieties viz. C(10)/N(2)/N(3)/C(1 1)/ S(1)/N(4)/N(5)/C(12) in A and B show some variations in planarity, as evidenced by a maximum deviation of0. 101(3) A for N(4A) in molecule A and a maximum deviation of 0.028(3) A for N(2B) in molecule B. This clearly shows that the central thiocarbohydrazone core is almost planar in molecule B and a slight deviation from planarity for the same core of molecule A. However the thiocarbohydrazide core N(2)/N(3)/C(l1)/S(1l)/N(4)/N(5) of molecule A is almost planar with a maximum deviation of -0.055(3) A for N(4A). 61
Chapter 2 Table 2.5. Hydrogen bonding geometry and C—H---1: interactions of H2L3. D—H---A D—H (A) H---A (A) D---A (A) D_H...A() 1 A) N(3A)—H(3AN) N(4A)—H(4AN)- -N(6A) N(4A)—H(4AN)- -N(2A) N(3B)—H(3BN)- -N(lB) N(4B)—H(4BN)--N(6B) N(4B)—H(4BN)--N(2B) 0.79(4) 0.85(3) 0.85(3) 0.86 0.85(4) 0.85(4) 2.15(4) 2.01(3) 2.21(3) 2.02 1.96(4) 2.20(4) 2.700(5) 2.688(5) 2.558(5) 2.692(5) 2.646(4) 2.572(5) 128(4) 137(3) 105(3) 134 136(3) 107(3) C(8A)—H(8A)---Cg(8)’ 0.93 2.59 3.3821(44) 143 C(18A)—H(18A)---Cg(7)” 0.93 2.96 3.8008(46) 151 C(19A)—H(19A)---Cg(9)” 0.93 2.92 3.6909(45) 141 D= donor, A=acceptor; Symmetry codes: (a) -x, -y, 1 - z; (b) 1-x, l-y, 1-z. Each molecule contains two ten membered quinoline rings comprising atoms N(l), C(l)-C(9) and N(6), C(13)-C(21). There are eight centroids viz. Cg(1) and Cg(7) [comprising atoms N(1), C(l), C(6), C(7), C(8), C(9) with maximum deviations of 0.025(3) A for C(9A) and 0.011(4) A for C(9B)], Cg(2) and Cg(8) [comprising atoms N(6), C(13), C(14), C(15), C(16), C(21) with maximum deviations of 0.018(4) A for C(2lA) and -0.008(4) A for C(15B)], Cg(3) and Cg(9) [comprising atoms C(l), C(2), C(3), C(4), C(5), C(6) with maximum deviations of 0.020(4) A for C(1A) and 0.006(4) A for C(2B)], and Cg(4) and Cg(l0) [comprising atoms C(16), C(17), C(18), C(19), C(20), C(21) with maximum deviations of 0.019(5) A for C(19A) and 0.014(4) A for C(16B)], which are parts of four quinoline rings of the two forms A and B of compound HZL3. In molecule B each of the two quinoline rings are in separate planes, with maximum deviations of -0.018(4) A for C8B and 0.034(4) A for C(19B), and makes an angle of 5.19(11)° each other; while in molecule A both quinoline rings show slight deviation in planarity compared to that in molecule B. Here the quinoline rings, Cg(5) involving N(1A) and Cg(6) involving N(6A), show maximum mean plane deviations of 0.057(5) A for C(4A) and 0.050(5) A for C(19A) respectively. The dihedral angles 3.3(2)° between the mean planes of Cg(1) and Cg(3) and 2.7(2)° 62
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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
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 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
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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 (
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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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Chapter 4 various aspects like bond
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C0pper(ll) complexes Table 4.6. Sel
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,____ p _p C0pper(H) complexes from
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Ed. Engl. 31 (1992) 733. 7___7 7 7
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__ ,_ f W C 0pper(l1) complexes Che
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-_ FIVE CHAPTER Spectral and magnet
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__ g_ _g g H g __ Manganese(II) com
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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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Self-assembled Transition Metal Coordination Frameworks of ...

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