Self-assembled Transition Metal Coordination Frameworks of ...

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My speciaf t/ianfis to (Dr. L.7(. ‘Iiiompson, 9Vlemoria[ ‘University, St. ]ofzn’s, Wewfoundmnd, Canada for providing me tfie 514/’1g5vt’U9\’4.1 software and usefuf discussions. I wisfi to tfianfi (Dr. (Priya Srinivas, RQCQ, ’I7iiru'uanant/iapuram, and 9‘l'lr. Rafiesfi for anticancer studies. I express my gratitude fiere to (Dr. flfexa-nder ‘Vargfiese ’(/aia§1an, (Department of Cfiemistry, St. 5teplien’s College, Qatlianapuram for teacfiing pfiysicaf cliemistry fundamentals and snowing tlie meaning of commitment. Here I am Happy to mention my sincere tfianlis to alt my teacfiers from my sc/ioof time. I express my sincere gratitude to (Dr. (RT. Rap/iea[ for firs cooperation and fielping attitude. I am very mucli tfianfifuf to (Dr. Rofiitfi Q’. ]o/in, ®epartment of (ffiemistry and jlpplied Cfiemistvy, Institute of 9\/aturaf Sciences, flanyang ‘University, flnsan, Sout/i Korea, for necessary /ielp and encouraging comments. My sincere tlianfis to 9\/lr. firun ‘V, (Dr. Ramanatfian and (Dr. Rad/iifia for friendsfiip and "w/ioflefiearted support. I sincerefiz appreciate tfie friendsfiip and encouragement of5ree1Qantfi (I/.3. and @rem Q>ra6fial{ar. I -wisfi to tfianfimy friend fMr. (Prinson for WZMR measurements and for warm support. I acfinowledge t/iefriendsfiip and support of my seniors ®r. ’(/arug/iese Qliilip and (Dr. 51/lartfia/{uttty josep/i. I express my speciaf tfianlis to my laiimates Lafy miss, jayafiumar sir, (Dr. Seena, (Dr. Suni, Mini, Suja, Srees/ia, Leji, Sfieeja, Wancy, Reena and Ranjuslia for providing a worliatmospfiere. I afso appreciate many researcfi scliolars, 5% Tfiifl SM ‘Tecfi and 9% Sc students wfio Have created a pleasant atmospfiere. I am mucfi o6[zged to tfie autfiorities of CU5/’l‘T for providing 5etter worfiing atmospfiere, [i6ra-ry and internet facifities. Last 6ut not [east I express my fieartify gratitude to my motlier, fatfier and relatives for tfieir love and encouragement. 21501/e all I praise tfie Lord Sriman Waraya-na, for compassion, unlimited filessings and for tfie success of t/iis endeavor. 91/lanoj (E.
PREFACE In its method, chemistry is a science of interactions, of transformations and of models. In its object, the molecule and the material, chemistry expresses its creativity. Chemical synthesis has the power to produce new molecules and new materials, with new properties. The appearance of supramolecular chemistry in the late 20"‘ century stimulated new thinking about the relationship of chemistry with biology, that biology and other higher sciences may be considered as emerging out of this new chemistry. The roots of supramolecular chemistry extend into organic chemistry, coordination chemistry and metal ion ligand complexes, physical chemistry, material science and biology. These wide horizons of supramolecular science are a challenge and a stimulus to the creative imagination of the chemist. However, chemistry is not limited to systems similar to those found in biology, but is free to create novel species and to invent processes. This Ph. D. thesis is mainly concemed with the coordination chemistry of some novel selected transition metal complexes of suitably substituted carbohydrazones and thiocarbohydrazones, with a view to self-assembled molecular square grid architectures, carried out during the period of my research from January 2004 to October 2007. The work presentation comprises reports of relevant related results published so far into a consistent and useful structure as far as that are possible. I hope the work comes up to its premises and proves useful though there remains, however, a lot to be done. Interesting anticipation are due to ideal opportunities that it can provide some steps into the fascinating world of supramolecular chemistry through symmetrical metallosupramolecular square grid complexes and related studies. Symmetry is everywhere we look in nature. Nature like symmetry as there seems to be a lot of symmetrical objects. In lines to those beautiful symmetrical structures of macro world, building beautiful framework molecules is a subject of keen interest in all branches of synthetic chemistry especially because of their potential applications. The current work focuses on building beautifiil molecular
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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
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Page 23 and 24: Chapter I g g _ exhibit considerabl
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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
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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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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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