Binuclear phthalocyanines [Elektronische Ressource] : synthesis, characterisation and optical limiting properties = Binukleare Phthalocyanine / vorgelegt von Mário Calvete

Www

Informations

• Publié par: eberhard_karls_universitat_tubingen
• Publié le: 01 janvier 2004
• Nombre de lectures: 32
• Langue: Deutsch

Extrait

Binuclear Phthalocyanines:
Synthesis, Characterisation and Optical Limiting Properties


Binukleare Phthalocyanine:
Synthese, Charakterisierung und Optical Limiting Eigenschaften



Dissertation




der Fakultät für Chemie und Pharmazie
der Eberhard-Karls-Universität Tübingen



zur Erlangung des Grades eines Doktors
der Naturwissenschaften






2004






vorgelegt von

Mário Calvete







































Tag der mündlichen Prüfung: 22. Januar 2004
Dekan: Prof. Dr. H. Probst
1. Berichterstatter: Prof. Dr. h. c. M. Hanack
2. Berichterstatter: Prof. Dr. G. Häfelinger






2











































Die vorliegende Arbeit wurde am Institut für Organische Chemie der Eberhard-Karls-
Universität Tübingen unter der Anleitung von Prof. Dr. Dr. h. c. M. Hanack durchgeführt,
dem ich für seine Unterstützung und sein Interesse herzlich danke.




3



















Für meine Eltern, immer.


























4
Index
I General part 9
1. Introduction 10
10 2. Phthalocyanines and related macrocycles
2.1 Historical parenthesis 10
2.2 Absorption spectra of phthalocyanines 11
2.3 General synthesis of phthalocyanines 12
2.4 Solubilization of phthalocyanines 13
15 2.5 Expansion of the π-system: benzoannulated phthalocyanines
3. Optical limiting: A nonlinear optical effect 17
3.1 Nonlinearity of the Optical Limiting Effect 18
3.2 Optical limiting: mechanisms and models 20
3.3. Phthalocyanines and optical limiting 21
3.4. Naphthalocyanines and optical limiting 27
3.5. Z-scan technique 28
3.5.1. Some examples 29
II Aim of the work 32
34 III - Results and discussion
1. Synthesis of binuclear phthalocyanines 34
1.1. Synthesis of [2,3,9,10,16,17-hexa-2-ethylhexyloxy-25,26- dicyano]
phthalocyaninato nickel 11 39
1.1.1. Synthesis and spectroscopic characterization of phthalocyanine 4 40
1.1.2. Synthesis and spectroscopic characterization of phthalocyanine 9 41
1.1.3. Synthesis and spectroscopic characterization of phthalocyanine 10 41
1.1.4. Synthesis and spectroscopic characterization of phthalocyanine 11 42
1.2. Ni/Ni binuclear metal-phthalocyanines 12 and 13 42
1.2.1. Synthesis and spectroscopic characterization of binuclear phthalocyanines 12 42
and 13
1.3. Compounds (14 and 15) - Ni/Cu binuclear metal-phthalocyanines 47
1.3.1. Synthesis and spectroscopic characterization of binuclear phthalocyanines 14 47
and 15
1.3.1.1. Atomic Absorption Spectroscopy - a simple and effective method for
qualitative and quantitative determination of metals 48
2. Binuclear metal phthalocyanines for optical limiting purposes 51
2.1. Synthesis of an unsymmetric functionalized magnesium phthalocyanine
[2,3,9, 10,16,17-hexa-2-ethylhexyloxy-25,26-dicyano] magnesium phthalocyanine
19 52
2.1.1. Synthesis and spectroscopic characterization of phthalocyanine 16 53
2.1.2. Synthesis and spectroscopic characterization of phthalocyanine 17 54
2.1.3. Synthesis and spectroscopic characterization of phthalocyanine 18 55
2.1.4. Synthesis and spectroscopic characterization of phthalocyanine 19 55
2.2. Binuclear metal phthalocyanines with InCl and GaCl as central moieties 56
2.2.1. Synthesis of binuclear phthalocyanines 20-23 56
2.2.2. Spectroscopic characterization of binuclear phthalocyanines 20-23 58
3. Synthesis of octaalkoxy substituted Ga, In and Tl Pc's 62
3.1. Isolation and spectroscopic characterization of Mg phthalocyanine 24 63
3.2. Synthesis and spectroscopic characterization of metal free
phthalocyanine 25 63
3.3. Indium (26), gallium (27) and thallium (28) octasubstituted Pc's 64
3.3.1. Synthesis and spectroscopic characterization of phthalocyanines 26 and 27 64
5 3.3.2. Synthesis and spectroscopic characterization of phthalocyanine 28 66
4. Optical limiting measurements for the In/In binuclear Pc 22 68
IV - SUMMARY 72
V - EXPERIMENTAL PART 75
75 1. General comments
2. Synthesis 76
2.1. Synthesis of precursors 76
2.1.1. 4,5-bis(2-ethyl-hexyloxy)-1,2-phthalonitrile 1 76
2.1.1.1 1,2-bis(2-ethyl-hexyloxy)benzene 76
2.1.1.2 1,2-dibromo-4,5-bis(2-ethyl-hexyloxy)benzene 77
2.1.1.3 4,5-Bis(ethylhexyloxy)-1,2-phthalonitrile 1 78
2.1.2. 1,4-Epoxy-1,4-dihydronaphthalene-6,7-nitrile 2 78
2.1.2.1 6,7-dibromo-1,4-epoxy-1,4-dihydronaphthalene 78
2.1.2.2. 1,4-Epoxy-1,4-dihydronaphthalene-6,7-nitrile 2 79
2.2. Synthesis of the benzoannulated unsymmetrically substituted nickel
phthalocyanine 11 80
2.2.1. [2,3,9,10,16,17-hexa(2-ethylhexyloxy)-23,26 - dehydro-23,26-epoxybenzo-
phthalocyaninato]nickel (4) 80
2.2.2. [2,3,9,10,16,17-hexa(2-ethylhexyloxy)-23,26-dihydro-23,26-epoxybenzo-
24,25-tetracyclone-phthalocyaninato]nickel adduct 9 81
2.2.3. [2,3,9,10,16,17-hexa(2-ethylhexyloxy)-23,26-dihydro-23,26-epoxybenzo-
25,26-fumaronitrile-phthalocyaninato]nickel ad