Suraj Mal

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Chapter 2 2.1 2.2 2.3 2.4 2.4.1. 2.4.2. 2.4.3. 2.5 2.6 2.7 2.7.1. 2.7.2. RESULTS AND DISCUSSIONS………………………………………... Lanthanide complexes based on tetrazolates…………………………. Synthesis of pyridine-oxide tetrazole………………………………….. Characterization of pyridine-oxide tetrazolate ligand……………….. Synthesis and characterization of lanthanide pyridine-oxide tetrazolate complexes…………………………………………………… Photophysical studies of HPTO and lanthanide pyridine-oxide tetrazolate complexes I and II…………………………………………. Ligand centered luminescence HPTO…………………………………… Absorption and excitation characteristics of complexes I and II……….. Metal centered luminescence..................................................................... Synthesis and spectral characterization of auxiliary phosphine oxide coligands………………………………………………………………… Synthesis and characterization of ternary complexes of Eu(PTO)3 with selected phosphine oxides………………………………………… Photophysical studies of ternary europium-tetrazolate complexes III to XIII…………………………………………………………………… Absorption and excitation characteristics………………………………. Metal centered luminescence……………………………………………. Chapter 3 Lanthanide complexes based on isoxazolonates………………………. 105 3.1 3.2 3.2.1. 3.2.2. 3.3 3.3.1. 3.3.2. 3.4 3.5 3.5.1 Synthesis and characterization of synthesized isoxazolonates……….. Synthesis and characterization of lanthanide isoxazolonate complexes………………………………………………………………... tris-(3-phenyl-4-benzoyl-5-isoxazolone) Eu(III) and Tb(III) complexes... tris-(4-isobutyryl-3-phenyl-5-isoxazolone)Tb(III) complex....................... Photophysical studies of lanthanide tris-isoxazolonate complexes XIV, XV and XVI………………………………………………………. Absorption and excitation characteristics………………………………. Metal centered luminescence……………………………………………. Synthesis and characterization of ternary isoxazolonate complexes with neutral auxiliary sensitizing coligands………………………….. Photophysical studies…………………………………………………… Spectroscopic studies of ternary Eu(III) isoxazolonate (PBI) complexes 70 70 70 70 73 77 77 78 80 83 87 96 96 100 105 107 107 108 109 109 111 115 118 vi
3.5.2. 3.6 3.6.1. 3.6.2. Chapter 4 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 (XVII to XIX)……………………………………………………………... Metal centered luminescence……………………………………………. Spectroscopic studies of ternary Tb(III) isoxazolonate (IBPI) complexes (XX to XXII)………………………………………………... Absorption and excitation characteristics………………………………. Metal centered luminescence……………………………………………. EXPERIMENTAL……………………………………………………….. Methods and procedures……………………………………………….. General…………………………………………………………………... Synthesis of tetrazole 5-(2-pyridyl-1-oxide)tetrazole (HPTO)……….. Ligand based on isoxazoles…………………………………………….. Synthesis of phosphine oxide coligands (P1-P11)…………………….. Synthesis of lanthanide complexes based on tetrazolate ligand……... Synthesis of ternary-(tetrazolate)-Eu(III) complexes (III to XIII)…... Lanthanide complexes based on isoxazolonate ligand……………….. Europium ternary complexes with phosphine oxides based on 3- phenyl-4-benzoyl-5-isoxazolone (HPBI) ligand (XVII to XIX)……… Terbium ternary complexes with phosphine oxides based on 4- isobutyryl-3-phenyl-5-isoxazolone (HIBPI) ligand (XX to XXII)…… FINAL CONCLUSIONS AND PERSPECTIVES………………………. 141 118 119 122 122 123 126 126 126 127 127 129 131 132 136 138 139 vii
Page 1 and 2: INSTITUTE OF PHYSICAL CHEMISTRY POL
Page 3 and 4: Acknowledgements I am so fortunate
Page 5: TABLE OF CONTENTS INTRODUCTION…
Page 9 and 10: INTRODUCTION Excerpt from the FINEL
Page 11 and 12: AIM OF THE WORK Luminescence of lan
Page 13 and 14: acpy acylprazolones PMAP 1-phenyl-3
Page 15 and 16: PyTzH 2-(1H-tetrazol-5-yl)pyridine
Page 17 and 18: f transition, making direct photoex
Page 19 and 20: There are 295 (2S+1) ГJ spectrosco
Page 21 and 22: Figure 1.6. Emission spectra of som
Page 23 and 24: epresented in figure 1.7 and 1.8. E
Page 25 and 26: For appended coligand with tris-lan
Page 27 and 28: Nonradiative rate constant, can be
Page 29 and 30: through-space Forster-type mechanis
Page 31 and 32: thus play an important role in ener
Page 33 and 34: C H 3 C H 3 C H 3 C H 3 CF 3 CF 2 C
Page 35 and 36: showing maximum absorption waveleng
Page 37 and 38: C H 3 1 2 N N 5 3 4 O O 4-acetyl (P
Page 39 and 40: Recently, our group has published w
Page 41 and 42: group such as O, S, P etc. which ma
Page 43 and 44: which have been observed in the con
Page 45 and 46: R CN NaN 3 /ZnX 2 H 2 O, reflux Fig
Page 47 and 48: Later, Faccetti et. al. has reporte
Page 49 and 50: 1.5.4. Tetrazolate transition metal
Page 51 and 52: N O Ph O + O O O R R Figure 1.29. G
Page 53 and 54: Eu(III) with PTI and with several n
Page 55 and 56: emove quencher molecules from the f
Page 57 and 58:
Table 1.2. List of some N-donor col
Page 59 and 60:
H 3 CO OCH 3 H 3 CO O OCH 3 H 3 CO
Page 61 and 62:
Ternary lanthanide complexes contai
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of photons will be sufficiently hig
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emitting diodes (LED), optical fibe
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Some lanthanide ions, Ce(III), Pr(I
Page 69 and 70:
Luminescent immunoassay s Photodyna
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N N Ln(III) N N N N N N Ln = Eu(III
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displays in mobile phones, car ster
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Ln(III) [Eu(III) and Tb(III)] 1,3-d
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(1.1%). Diaz-Garcia et al. 188 stud
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in polar solvents. The mid and far-
Page 81 and 82:
The absorption spectra of 5-(2-pyri
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spectral band at 450 cm -1 , 400 cm
Page 85 and 86:
In complex I the central Eu(III) io
Page 87 and 88:
coordination of oxygen and nitrogen
Page 89 and 90:
expected bands for the 5 D0→ 7 F0
Page 91 and 92:
The short lifetime values obtained
Page 93 and 94:
We choose aliphatic and aromatic su
Page 95 and 96:
300 nm region, while P2 shows two b
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V C48H36EuN15O5P2 VI C48H37EuN16O5P
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of Eu(III) ion with N of tetrazole
Page 101 and 102:
Similar to complex I, the crystal g
Page 103 and 104:
O(11)=P(2) .... P(3)=O(8) N(21)-C(1
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which lie in the of 300-250 nm rang
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Absorbance/Intensity(a.u.) Absorban
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intensity of 5 D0→ 7 F0-4 bands w
Page 111 and 112:
5 D0→ 7 F2 and 5 D0→ 7 F4 trans
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(B) Figure 2.28. Proposed energy mi
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coefficient of HPBI (ε = 9.14 x 10
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3 N O O C H 3 H O CH 3 3NaOH, Tb(NO
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Intensity(a.u.) 1,0 0,8 0,6 0,4 0,2
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Intensity(a.u.) 1,0 0,8 0,6 0,4 0,2
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3.4. Synthesis and characterization
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The IR spectra of complexes XVI to
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(PBI) and the corresponding phosphi
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We observed an enhancement in photo
Page 131 and 132:
Table 3.8. Absorption wavelength ma
Page 133 and 134:
ligands which results in energy dis
Page 135 and 136:
4.2. Synthesis of ligands Ligand ba
Page 137 and 138:
4.4. Synthesis of phosphine oxide c
Page 139 and 140:
stirred with methanol (2 x 40 mL) t
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N N N N O N 3 Eu.(H 2 O) 3 (RP=O) n
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IR (KBr) νmax: 3315 (O-H str.), 30
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Eu(PBI)3(H2O)3.5 (complex XIV) N O
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Eu(PBI)3.(P7)2.(H2O)5 (complex XVII
Page 149 and 150:
FINAL CONCLUSIONS AND PERSPECTIVES
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Suraj Mal

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