Self-assembled Transition Metal Coordination Frameworks of ...

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_g 7 Introduction is associated with a spin angular momentum m, = +‘/2, leading to a doubly degenerate spin state in the absence of a magnetic field. When a sufficient magnetic field is applied, this degeneracy is removed, and the energy difference between two resultant states is given [91] by, AE = hv = g/3H where h is Planck’s constant, v is the frequency, g is the Lande splitting factor, ,6 is the electron Bohr magneton and H is the magnetic field. The static spin Hamiltonian used to describe the energies of states of a paramagnetic species in the ground state with an effective electron spin S and m nuclei with spins I is given by [92] F1 -1? +151 ..+H +1-Al. +1? 0 _ 1-tz zrs HF .-\-z A-"Q Where, UH - electron Zeeman interaction, H ZFS - zero-field splitting, H HF hyperfine interactions between the electron spins and the m nuclear spins, H NZ nuclear Zeeman interactions and H NQ - nuclear quadrupole interactions for I > ‘/2. EPR is an important spectroscopic tool in experimental studies of systems containing unpaired electrons. The traditional application areas for EPR include studies of transition metal complexes, stable organic radicals, transient reaction intermediates, as well as solid state and surface defects. EPR spectroscopy measures differences between magnetic energy levels and this is the principal difference from the magnetic susceptibility measurements, which measures the Boltzmann occupation of all energy levels [93]. In many cases, the extreme sensitivity of EPR allows experimental access to electronic structure and molecular environment parameters, which would be impossible to measure otherwise. The structure of the EPR spectrum depends upon (a) the g-tensor anisotropy, (b) the presence of the hyperfine interaction of the central atom nuclear spin with the electron spin (the AM-i€11SOI‘), (c) the presence of the superhyperfine interaction of the ligand donor atom nuclear spins with the 25
Chapter I ,,_ g electron spin (the AI‘-tensors), (d) the appearance of satellites among which the forbidden transitions may occur, (e) the nuclear quadrupole effects, (f) the zero-field splitting (ZFS) and (g) the exchange (spin-spin) interactions of the magnetic centers [93]. Several factors influence the line-width of the EPR spectra, as the dipolar interaction, the exchange interaction, and the zero field splitting. The effect of the dipolar interaction is the broadening of the main line of the spectrum. When the exchange interaction is present, a narrowing of the bands could be observed. If the dipolar interaction is more important than the exchange interaction, a broadening of the spectra will be attended. Additional broadening mechanisms are the hyperfine coupling and the single-ion ZFS effects [94]. EPR spectrum of a compound reveals some distinct features of the structure of the paramagnetic molecule. For example, for Cu(Il) complexes, the factors that determine the type of EPR spectrum observed are: (a) nature of the electronic ground state (b) the symmetry of the effective ligand field about the Cu(ll) ion (c) the mutual orientations of the local molecular axes of the separate Cu(II) chromophores in the unit cell. The factors (a) and (b) deal with the mode of splitting of the five-fold degenerate 3d orbitals by crystal fields of octahedral and tetrahedral symmetries which are inverse of each other. The orbital sequences of the various stereochemistries determine their ground states. The vast majority of Cu(lI) complexes give rise to orbitally non-degenerate ground states involving a static form of distortion and a dx; , . ‘y ground state; a substantial number of complexes have a d_, ground state and a few have a d_,_,. ground state. It depends on the nature of the ligands regarding their rt bonding potential. The third factor (c) determines the amount of exchange coupling present, which is the major factor in reducing the amount of stereochemical information available from the EPR spectra [95]. 26
Page 1 and 2: 7,2/H5 Self-assembled Transition Me
Page 3 and 4: , Phone orr. 0484-2575804 ; Phone R
Page 5 and 6: ‘ilC7(,'NO’WLQ'I(D QEMEWT In tl
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: Chapter I W__‘ _ 1.6.6. MALDI MS
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
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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-
Page 100:
3.3.2. IR and electronic spectral s
Page 103 and 104:
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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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
Page 290:
2-Hydroxyacetophenone 4-phenylthios
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