Preparation, characterization and X-ray crystal structures of new axially functionalized phthalocyanines and phthalocyanine modified SBA-15 materials [Elektronische Ressource] = Darstellung, Charakterisierung und Kristallstrukturen neuer axial funktionalisierter Phthalocyanine und Phthalocyanin-modifizierter SBA-15-Materialien / Wael Mahmoud Ahmed Darwish

Kunde

Informations

• Publié par: philipps-universitat_marburg
• Publié le: 01 janvier 2006
• Nombre de lectures: 101
• Langue: English
• Poids de l'ouvrage: 6 Mo

Extrait

Preparation, Characterization and X-ray Crystal Structures of
New Axially Functionalized Phthalocyanines and Phthalocyanine
Modified SBA-15 Materials

Darstellung, Charakterisierung und Kristallstrukturen neuer
axial funktionalisierter Phthalocyanine und Phthalocyanin-
modifizierter SBA-15 Materialien




Dissertation

Zur
Erlangung des Doktorgrades
der Naturwissenschaften
(Dr. rer. nat)


dem
Fachbereich Chemie
der Philipps-Universität Marburg



Vorgelegt von

Wael Mahmoud Ahmed Darwish

aus Lekalyoubia




Marburg/Lahn 2006









Die vorliegende Arbeit entstand in der Zeit von Oktober 2001 bis Februar 2006 unter der
Leitung von Herrn Prof. Dr. J. H. Sundermeyer am Fachbereich Chemie der Philipps-
Universität Marburg.




Vom Fachbereich Chemie der Philipps-Universität Marburg als Dissertation angenommen am
15. Februar 2006





1.Gutachter: Prof. Dr. J. H. Sundermeyer

2. Gutachter: Prof. Dr. W. Massa


Tag der Disputation: 02 März 2006










To my Parents, my Wife,
my Daughter (Rawan),
and every one taught me Chemistry
To my Homeland
Egypt
Acknowledgment

I wish to express my deepest thanks to Prof. Dr. J. H. Sundermeyer, Professor of
Chemistry, Philipps-Universität Marburg, for supervision, valuable guidance and fruitful
discussions.

I’m grateful to Dr. K. Steinbach for (MS) measurements, Dr. O. Burghaus (ESR), Dr.
Weller and Mr. Schmock (RS), Mrs. Bahmann (FTIR), Mr. Lennick and Mr. Ulrich (EA), Dr.
Xie (NMR-500 MHz), Mr. Beifus (GPC), and Dr. Schaper (TEM). I’m also grateful to Prof.
Dr. W. Massa, Dr. K. Harms and Mrs. G. Geiseler for carrying out the X-ray crystallographic
measurements of some isolated single crystals.

I would like to thank Prof. Dr. W. Rühle and his research group (Dr. S. Chatterjee and
K. Hankte) at Physics Department, Philipps-Universität Marburg for carrying out the
photoluminescence measurements of some compounds and together discussion of the results
within a cooperation project. I’m very grateful to Prof. Dr. S. Schlecht, Professor of
Chemistry, Freie-Universität, Berlin and Prof. M. Fröba, Professor of Chemistry, Justus-
Liebig-Universität, Gießen for fruitful discussions in the field of mesoporous materials.

I would like also to thank Prof. Dr. Mahmoud A. Abd El-Ghaffar, Prof. of Polymers
and Pigments, Dr. Elham A. Youssef, and Prof. Dr. A. S. Badran; National Research Centre,
Cairo, Egypt for support and kind help.

My thanks are extended to my colleagues in AK Sundermeyer. I would like also to
thank my colleagues at Philipps-Universität: Dr. S. Agarwal, M. Becker, S. Horst, and Frau
M. Gerlach for kind help. Table of Contents

1. Introduction

1.1 History of Phthalocyanines …………………………………………………........ 1
1.2 Structure of Phthalocyanines …………………………………………………… 1
1.3 Synthesis and Purification of Phthalocyanines ...……………............................... 2
1.4 Mechanism of Phthalocyanine Formation …………………………………......… 3
1.5 Crystal Structure of Phthalocyanines ……………………………………………. 5
1.6 The Electronic Structure of Metal Phthalocyanines …………………………...... 7
1.7 Applications of Phthalocyanines ………………………………………………… 7
1.8 Titanium Phthalocyanines
1.8.1 Dichlorotitaniumphthalocyanine [PcTiCl ] ……………….......................… 8 2
1.8.2 Oxotitaniumphthalocyanine [PcTiO] …………………....................……… 9
1.9 Titanium Porphyrins ………………………………………………...................… 13
1.10 Phthalocyanines and Porphyrins of Mo,W and Re ……………………………… 15
1.11 Phthalocyanine Polymers ……………………………………………………...… 17
1.12 Mesoporous Molecular Sieve Materials
1.12.1 Preparation of SBA-15 and MCM-41 Materials ………………………. 19
1.12.2 Preparation of Titanium Containing SBA-15 and MCM-41 …………... 20
1.12.3 Properties of Mesoporous Molecular Sieves …………………………... 21
1.12.4 Phthalocyanine Modified Mesoporous Molecular Sieves …………….. 22
1.12.5 Characterization of MPc Modified Mesoporous Molecular Sieves …… 27
1.12.6 Applications of MPc Modified Mesoporous Molecular Sieve Materials 27
1.13 Photoluminescence of Phthalocyanines …………………………………………. 28
1.14 Phthalocyanines as Laser Pigments ……………………………………………… 29

2. Results and Discussions

2.1 Titanium Phthalocyanines

2.1.1 Synthesis of Imido-TiPc (2) and Ureato-TiPcs (3a-d) ……………........... 30
2.1.2 Mechanism for the reaction of [PcTiO] (1) with the arylisocyanates ......... 31
2.1.3 Characterization of the Imido-TiPc (2) and Ureato-TiPcs (3a-d) ……...... 33
2.1.4 Crystal Structure of [PcTi(NDip)] (2) ……………………………………. 40 2.1.5 Crystal Structures of [PcTi(diarylureato)] (3a) and (3b) ………………… 44
2.1.6 Reaction of [PcTi(diarylureato)] with H S ………………………………. 49 2
2
2.1.7 Crystal Structure of [PcTi(η -S )] (5) ……………………………………. 50 2
2.1.8 Preparation of [PcTiS] (4) starting with [PcTiO] ………………………... 53
2.1.9 Synthesis of [PcTi{(NH) C H }] (6) …………………………………….. 54 2 6 4
2.1.10 Synthesis of trans-[PcTi(OSiPh ) ] (7) ……………………………........... 56 3 2
2.1.11 Crystal Structure of trans-[PcTi(OSiPh ) ] (7) ………………………….... 58 3 2

2.2 Molybdenum Phthalocyanines

2.2.1 Synthesis of [PcMo(NR)Cl] (9a,b) …………………………………….... 61
2.2.2 Characterization of [PcMo(NR)Cl] (9a,b) ……………………………..... 63
2.2.3 ESR Spectra of [PcMo(NR)Cl] (9a,b) …………………………………... 65
2.2.4 Crystal Structure of [PcMo(NR)Cl] (9a) ……………………………….... 68

2.3 Tungsten Phthalocyanines

2.3.1 Synthesis of [PcW(NR)Cl] (11a,b) ……………………………………… 72
2.3.2 Characterization of [PcW(NR)Cl] (11a,b) ………………………………. 72
2.3.3 ESR Spectra of [PcW(NR)Cl] (11a,b) …………………………………... 73
2.3.4 Synthesis of [(Cl Pc)W(NR)] (13a-c) ……………………………………. 77 2
2.3.5 Characterization of [(Cl Pc)W(NR)] (13a-c) …………………………….. 79 2

2.4 Rhenium Phthalocyanines

2.4.1 Synthesis of [PcRe(NR)Cl] (15a,b) ……………………………………… 81
2.4.2 Characterization of [PcRe(NR)Cl] (15a,b) ……………………………… 82

2.5 Phthalocyanine Polymers

2.5.1 Synthesis of Phthalocyanine Polymers (16-18) ………………………….. 84
2.5.2 Characterization of Phthalocyanine Polymers (16-18) …………………... 86

Time-resolved Photoluminescence …………………............................................ 90 2.6

2.7 Phthalocyanine Modified SBA-15 Mesoporous Silica Materials …………….. 94

105 3. Summary ………………………………………………………………………………

4. Experimental Work

114 4.1 Materials and Methods ………………………………………………………...

4.2 Techniques of Characterization …………………………………………............ 115

4.3 Preparation of Titanium Phthalocyanines

4.3.1 Preparation of [PcTi(NDip)] (2) ………………………………………… 118
4.3.2 Preparation of [PcTi(diarylureato)] (3a-d) ……………………………… 119
4.3.3 Preparation of [PcTiS] (4) ………………………………………………... 124
4.3.4 Preparation of [PcTi(η-S )] (5) …………………………………………... 125 2
4.3.5 Preparation of [PcTi{(NH) C H }] (6) …………………………………... 127 2 6 4
4.3.6 Preparation of trans-[PcTi(OSiPh ) ] (7) ………………………………… 127 3 2

4.4 Preparation of Molybdenum Phthalocyanines

t
4.4.1 Preparation of [PcMo(N Bu)Cl] (9a) …………………………………….. 129
4.4.2 Preparation of [PcMo(NMes)Cl] (9b) ……………………………............ 130

4.5 Preparation of Tungsten Phthalocyanines

t
4.5.1 Preparation of [PcW(N Bu)Cl] (11a) …....................................………….. 131
4.5.2 Preparation of [PcW(NMes)Cl] (11b) ….................................................... 132
4.5.3 Preparation of [(Cl Pc)W(NR)] (13a-c) ….................................................. 132 2

4.6 Preparation of Rhenium Phthalocyanines

t 4.6.1 Preparation of [PcRe(N Bu)Cl] (15a) …..................................................... 134
4.6.2 Preparation of [PcRe(NMes)Cl] (15b) ….................................................... 134

4.7 Phthalocyanine Polymers

4.7.1 Preparation of Polyoxotitaniumphthalocyanine (16) …………………….. 135
4.7.2 Preparation of Polyimidomolybdenumphthalocyanine (17) ……………... 136
4.7.3 Preparation of Polyimidotitaniumphthalocyanine (18) …………………... 137
4.8 Time-resolved Photoluminescence Study of TiPcs …………………………….. 137

Preparation of Phthalocyanine Modified Silica Materials ……………............. 139 4.9

141 5. References ……………………………………………………………………………..


List of Abbreviations


AAS : Atom Absorption Spectroscopy
Calcd. : Calculated
CHN : Combustion analysis of mass %C, H, and N
ClB : Chlorobenzene
ClN : Chloronaphthalene
dme : 1,2-Dimethoxyethane
DSC : Differential Scanning Calorimetry
EA : Elemental Analysis
EI-MS : Electron Impact Mass Spectroscopy
EPR : Electron Paramagnetic Resonance
ESI-MS Electron Spra