Optical limiting effect of new synthesized phthalocyanines in solution and in solid state [Elektronische Ressource] / von Aneta Słodek

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Informations

• Publié par: universitat_bremen
• Publié le: 01 janvier 2010
• Nombre de lectures: 36
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Optical Limiting Effect of New Synthesized
Phthalocyanines in Solution and in Solid State






DISSERTATION

Zur Erlangung des Doktorgrades der Naturwissenschaften
-Dr. rer. Nat.-


vorgelegt dem Promotionsausschuß
des Fachbereichs 2 (Biologie/Chemie)
der Universität Bremen








von
Aneta Sdek







Bremen, Dezember 2010














































1. Gutachter: Prof. Dr. D. Wöhrle
2. Gutachter: Prof. Dr. P. Swiderek
Vorgelegt: Im Oktober 2010











































To my Sister and my Parents


Dla Katarzyny Kodziej
- wspaniaj siostry i przyjaciki
i moich rodzic
Acknowledgements

I would like to express my special acknowledgements to Professor Dieter Wöhrle for giving
me the opportunity to work in his group as a PhD student. I am grateful for the numerous
scientific meetings and his helpful suggestions and advices, and for his guidance as well as
for his encouragement during the scientific work. I am extremely indebted to him for his
patience, help, enthusiasm, optimism, and for the creation of great work atmosphere. Thank
you very much indeed.
I am especially grateful to Professor Petra Swiderek for her approval to be my co-supervisor.
I am also thankful to Dr. Günter Schnurpfeil and Dr. Andreas Hartwig for being my co-
examiners.
I would like to thank all the members of Professor Wöhrle group for pleasant and kind
atmosphere, in particular, my special acknowledges to Dr. kasz pok for the stimulating
discussion and useful advices in experimental work, and his help whenever I needed; Sergey
Makarow for the scientific discussions and comments, Natasha Baziakina for help in
preparation of sealed ampoules and for great time spent together during her staying in
Bremen, Angela Wendt for an tremendous technical support. To Dr. Dülcks, I thank for Mass
Spectral measurements.
I would like to thank Professor Blau from Department of Physics, Trinity College in Dublin
for possibility to carry out the z-scan measurements. I wanted to express my gratitude to
James Doyle and Sean O’Flaherty from Professor Werner Blau group who introduced me to
the use of z-scan technique in order to perform optical limiting measurements of my samples.
I am extremely grateful for your helpful suggestions and principally for all calculations you
made.
I would also like to thank the European Union Network under the contract HPRN-00020 for
financial support and the opportunity to participle in so fascinating and challenging project.
I am very grateful to my relevant and my friends, in particular to Katarzyna Miku for their
wonderful support.
Finally, I wish to express my sincere appreciation to my parents, Lucyna and Leopold Sdek,
and my sister, Katarzyna Kodziej for their assistance, great encouragement, motivation and
faith in me. Their unreserved love and enormous support gave me strength to complete my
work. I cannot tell how much I am grateful to them.
Contents
ACKNOWLEDGEMENTS IV
LIST OF STRUCTURES IX
LIST OF ABBREVIATIONS XII
LIST OF SYMBOLS AND PHYSICAL TERMS XIV
PUBLICATIONS AND PRESENTATIONS XV
1. AIMS OF THE THESIS AND SCIENTIFIC APPROACH 1
1.1 References 2
2. PHTHALOCYANINES 4
2.2 General synthesis of phthalocyanines 5
2.2.1 Synthesis of metal-free phthalocyanines 5
2.2.2 metal-containing phthalocyanines 6
2.2.3 Synthesis of axially substituted phthalocyanines 8
2.3 Mechanism of phthalocyanine formation 9
2.4 Optical properties of phthalocyanines 12
2.4.1 Optical properties of phthalocyanines in solution 12
2.4.2 operties of phthalocn the solid state 14
2.5 References 15
3. NONLINEAR OPTICAL PROPERTIES OF PHTHALOCYANINES 18
3.1 Optical limiting phenomenon 18
3.2 Experimental techniques 23
3.3 Phthalocyanines as optical limiters 24
3.3.1 Structural factors affecting optical liming properties of phthalocyanines 26
3.3.1.1 Effect of the central metal atom on optical limiting properties of phthalocyanines 28
3.3.1.2 Effect of peripheral substituents on nonlinear properties of phthalocyanines 29
3.3.1.3 Effect of the axial substitution on optical limiting properties of phthalocyanines 31
3.3.2 Optical limiting properties of phthalocyanines in thin films 33
3.4 References 35
VContents
4. SYNTHESIS AND CHARACTERIZATION OF PHTHALOCYANINE
COMPLEXES 39
4.1 Synthesis of phthalonitriles 39
4.2 Synthesis of tetra- and octa-substituted phthalocyanines 42
4.3 Synthesis of hexadeca-substituted phthalocyanines 66
4.4 Conclusion 87
4.5 References 87
5. PREPARATION AND CHARACTERIZATION OF FILMS OF
PHTHALOCYANINES EMBEDDED IN DIFFERENT POLYMERS 89
5.1 Methods of preparation of phthalocyanine films 89
5.2 Characterization of phthalocyanine films prepared by spin casting method 91
5.2.1 Films of tetra-substituted phthalocyanines 91
5.2.2 Films of octa-substituted phthalocyanines 104
5.2.3 Thin films of hexadeca-substituted phthalocyanines 108
5.3 Characterization of phthalocyanine films prepared by drop casting method 114
5.4 Conclusion 118
5.5 References 119
6. EXPERIMENTAL PART 121
6.1 Materials 121
6.2 Instrumental methods 121
6.3 Synthesis of phthalonitriles 121
6.3.1 Synthesis of 4-(4-nitrophenoxy)phthalonitrile (1) 121
6.3.2 Synthesis of 4-(4-formylphenoxy)phthalonitrile (2) 122
6.4 Synthesis of phthalocyanines 122
6.4.1 Synthesis of 2,9,16,23-tetrakis(4-formylphenoxy)phthalocyanine (3) 122
6.4.2 9,s(4-nitrophenoxy)phthalocyanine (4) 123
6.4.3 Synthesis of dichlorotin(IV) 2,9,16,23-tetrakis(4-nitrophenoxy)phthalocyanine (5) 124
6.4.4 Synthesis of dichlorotin(IV) 2,9,16,23-tetrakis(4-formylphenoxy)phthalocyanine (6) 125
6.4.5 Synthesis of dichlorogermanium(IV) 2,9,16,23-tetrakis(4-formylphenoxy)phthalocyanine (7) 126
6.4.6 Synthesis of dichlorotin(IV) hexadecachlorophthalocyanine (8) 127
6.4.7 anium(IV) hexadecachlorophthalocyanine (9) 128
6.4.8 Synthesis of dihydroxytin(IV) hexadecachlorophthalocyanine (10) 129
6.4.9 Synthesis of dihydroxygermanium(IV) hexadecachlorophthalocyanine (11) 130
VI Contents
6.4.10 Synthesis of difluorotin(IV) hexadecachlorophthalocyanine (12) 130
6.4.11 Synthesis of difluorogermanium(IV) hexadecachlorophthalocyanine (13) 131
6.4.12 Synthesis of bis(3,5-di-tert-butylphenoxy)tin(IV) hexadecachlorophthalocyanine (14) 132
6.4.13 -tert-)germanium(IV) hexadecachlorophthalocyanine (15) 132
6.4.14 Synthesis of dichlorotin(IV) hexadecafluorophthalocyanine (16) 133
6.4.15 Synthesis of dichlorogermanium(IV) hexadecafluorophthalocyanine (17) 134
6.4.16 Synthesis of dichlorotin(IV) 2,9,16,23-tetranitrophthalocyanine (18) 135
6.4.17 V) 1,8,15,22-tetranitropht19) 135
6.4.18 Synthesis of dichlorogermanium(IV) 2,9,16,23-tetranitrophthalocyanine (20) 136
6.4.19 Synthesis of dihydroxygermanium(IV) 2,9,16,23-tetranitrophthalocyanine (21) 137
6.4.20 Synthesis of dichlorogermanium(IV) 1,8,15,22-tetranitrophthalocyanine (22) 138
6.4.21 Synthesis of bis(3,5-di-tert-butylphenoxy)germanium(IV)
2,9,16,23-tetranitrophthalocyanine (23) 138
6.4.22 Synthesis of dichlorotin(IV) 2,3,9,10,16,17,23,24-octacyanophthalocyanine (24) 139
6.4.23 Synthesis of chloroindium(III) 2,9,16,23-tetrakis(tert-butyl)phthalocyanine (25) 140
6.5 References 141
7. PREPARATION OF FILMS OF PHTHALOCYANINES EMBEDDED IN
DIFFERENT POLYMERS 142
7.1 Materials 142
7.2 Instrumental methods 143
7.3 Preparation of phthalocyanine films 143
7.3.1 Films prepared by spin casting technique 143
7.3.2 Sol gel solution for drop coating 147
7.3.3 Films prepared by drop 147
7.4 References 148
8. OPTICAL LIMITING PROPERTIES OF PHTHALOCYANINE COMPLEXES IN
SOLUTIONS AND IN FILMS 149
8.1 Introduction 149
8.2 Equipment and conditions of optical limiting measurement 151
8.3 Optical limiting properties of phthalocyanine complexes in solution 155
8.3.1 Optical limiting properties of metal-free, dichloro-substituted germanium(IV) and tin (IV) 2,9,16,23-
tetrakis(4-formylphenoxy)phthalocyanines 155
8.3.2 Optical limiting properties of metal-free and dichlorotin(IV) 2,9,16,23-tetrakis(4-
nitrophenoxy)phthalocyanines in comparison with OL effect in dichlorotin(IV)
2,3,9,10,16,17,23,24-octacyanophthalocyanine 158
VIIContents
8.3.3 Optical limiting properties of tin(IV) and germanium(IV