Liquid crystalline copper(II) complexes of poly(propylene imine) dendrimers [Elektronische Ressource] / vorgelegt von Laura Torre Lorente

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Liquid Crystalline Copper(II) Complexes of Poly(propylene imine) Dendrimers Dissertation zur Erlangung des akademischen Grades Doktor der Naturwissenschaften (Dr. rer. nat.) der Fakultät für Biologie, Chemie und Geowissenschaften der Universität Bayreuth vorgelegt von Laura Torre Lorente aus Calatayud (Spanien) Bayreuth, Dezember 2007 Die vorliegende Arbeit wurde in der Zeit von September 2001 bis Dezember 2007 am Lehrstuhl für Makromolekulare Chemie I der Universität Bayreuth angefertigt. Vollständiger Abdruck der von der Fakultät Biologie, Chemie und Geowissenschaften der Universität Bayreuth genehmigten Dissertation zur Erlangung des akademischen Grades Doktor der Naturwissenschaften (Dr. rer. nat.). Die Pflichtexemplare stimmen inhaltlich mit der Fassung überein, für die die Druckgenehmigung erteilt wurde. Datum der Einreichung der Arbeit: 2. Januar 2008 Datum des wissenschaftlichen Kolloquiums: 13.Juni 2008 Prüfungsausschuß: Prof. Dr. A. Fery (Vorsitzender) Prof. Dr. H.-W. Schmidt (Erstgutachter) Prof. Dr. H. G. Alt (Zweitgutachter) Prof. Dr. R. Schobert Diese Arbeit wurde von der Deutschen Forschungsgemeinschaft – Sonderforschungsbereich 481 finanziell unterstützt. TABLE OF CONTENTS LIST OF ABBREVIATIONS AND SYMBOLS.......................................................................... V 1 INTRODUCTION..........................................................................
Publié le : lundi 1 janvier 2007
Lecture(s) : 32
Source : OPUS.UB.UNI-BAYREUTH.DE/VOLLTEXTE/2009/558/PDF/DISSERTATION_LAURA_TORRE_LORENTE.PDF
Nombre de pages : 236
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Liquid Crystalline
Copper(II) Complexes of
Poly(propylene imine) Dendrimers



Dissertation

zur Erlangung des akademischen Grades
Doktor der Naturwissenschaften (Dr. rer. nat.)
der Fakultät für Biologie, Chemie und Geowissenschaften
der Universität Bayreuth


vorgelegt von
Laura Torre Lorente
aus Calatayud (Spanien)

Bayreuth, Dezember 2007


Die vorliegende Arbeit wurde in der Zeit von September 2001 bis Dezember 2007 am
Lehrstuhl für Makromolekulare Chemie I der Universität Bayreuth angefertigt.
Vollständiger Abdruck der von der Fakultät Biologie, Chemie und Geowissenschaften
der Universität Bayreuth genehmigten Dissertation zur Erlangung des akademischen
Grades Doktor der Naturwissenschaften (Dr. rer. nat.). Die Pflichtexemplare stimmen
inhaltlich mit der Fassung überein, für die die Druckgenehmigung erteilt wurde.

Datum der Einreichung der Arbeit: 2. Januar 2008
Datum des wissenschaftlichen Kolloquiums: 13.Juni 2008


Prüfungsausschuß:
Prof. Dr. A. Fery (Vorsitzender)
Prof. Dr. H.-W. Schmidt (Erstgutachter)
Prof. Dr. H. G. Alt (Zweitgutachter)
Prof. Dr. R. Schobert


Diese Arbeit wurde von der Deutschen Forschungsgemeinschaft –
Sonderforschungsbereich 481 finanziell unterstützt.




TABLE OF CONTENTS

LIST OF ABBREVIATIONS AND SYMBOLS.......................................................................... V
1 INTRODUCTION......................................................................................................... 1
1.1 LIQUID CRYSTALS ......................................................................................................... 1
1.1.1 The Liquid Crystalline State.......................................................................................... 1
1.1.2 Thermotropic Mesomorphism ....................................................................................... 1
1.1.3 Mesophases.................................................................................................................... 4
1.1.4 Lyotropic Mesomorphism. ............................................................................................ 8
1.1.5 Metallomesogens........................................................................................................... 9
1.1.6 Liquid Crystalline Polymers, LCPs ............................................................................. 10
1.2 DENDRIMERS ............................................................................................................... 12
1.2.1 Definition and Structure .............................................................................................. 12
1.2.2 Synthesis, Purity, and Polydispersity........................................................................... 12
1.2.3 Dendrimer Behaviour in Solution: Conformation ....................................................... 13
1.2.4 Further Properties. Comparison to Conventional Polymers. ....................................... 14
1.2.5 Nitrogen containing Dendrimers: PPI, PEI, PAMAM, and PAMAMOS.................... 15
1.3 DENDROMESOGENS ..................................................................................................... 18
1.3.1 Shape Persistent Dendrimers ....................................................................................... 18
1.3.2 Dendromesogens with Anisometric Mesogenic Units................................................. 19
1.3.3 Dendromesogens with Microsegregating Structures ................................................... 21
1.3.4 Supramolecular Dendrimers ........................................................................................ 22
1.3.5 Metallodendromesogens.............................................................................................. 23
1.3.6 Liquid Crystalline Nitrogen Containing Dendromesogens. PAMAM, PPI, and PEI
Derivatives................................................................................................................... 23
1.3.7 Liquid Crystalline Metal Derivatives of PAMAM, PPI, and PEI Dendrimers............ 27
2 OBJECTIVES............................................................................................................ 29
2.1 MOTIVATION................................................................................................................ 29
2.2 WORKING PLAN........................................................................................................... 32
3 LIQUID CRYSTALLINE, DENDRIMERIC COPPER(II) COMPLEXES......................... 35
3.1 SYNTHESIS ................................................................................................................... 35
3.1.1 Ligands ........................................................................................................................ 35
3.1.2 Copper(II) Complexes. Series of Highest Copper Loading......................................... 35
3.1.2.1 THF-Series................................................................................................................... 36
3.1.2.2 -Butyrolactone/Chloroform Series............................................................................. 38
3.1.2.3 Dependence of the Highest Loading on the Generation.............................................. 38
3.1.3 Copper (II) Complexes. Series of Lower Copper Loading. Specific Preparative
Procedures ................................................................................................................... 39
nd
3.1.3.1 2 Generation Complexes........................................................................................... 39
st
3.1.3.2 1 Generation Complexes............................................................................................ 43
3.1.4 Preparation of a Copper Complex from Copper Tetrafluoroborate............................. 45
3.1.5 Conclusions ................................................................................................................. 46
i
g
3.2 MOLECULAR COMPOSITION: ELEMENTAL ANALYSIS ................................................. 47
3.3 MALDI-TOF-MS......................................................................................................... 53
3.3.1 MALDI-ToF-MS: Introduction ................................................................................... 53
st nd
3.3.2 MALDI-ToF-MS of the lower Generations. Butandiamide, 1 and 2 Generation
Copper(II) Complexes ................................................................................................. 55
3.3.3 MALDI-ToF-MS Defect Structures, Fragments and Copper Bridged Dimers............ 58
rd th
3.3.4 MALDI-ToF-MS of the Higher Generations. 3 to 5 Generation
Copper(II) Complexes ................................................................................................. 64
3.3.5 Ionisation of the Copper(II) Complexes in MALDI-ToF-MS ..................................... 65
3.3.6 Conclusions.................................................................................................................. 66
3.4 TRANSMISSION ELECTRON MICROSCOPY, TEM.......................................................... 68
3.5 FTIR-INFRARED SPECTROSCOPY................................................................................. 73
3.5.1 FT-Infrared Spectroscopy: Introduction ...................................................................... 73
3.5.2 FTIR-Spectrum of the Ligands .................................................................................... 74
3.5.3 FTIR-Spectrum of the Copper(II) Complexes............................................................. 76
3.5.3.1 Coordinating Groups in the Ligand: Amine or Amide ................................................ 77
3.5.3.2 Role of the Nitrate. Comparison with the Complex from Tetrafluoroborate............... 80
3.5.3.3 HNO : Tertiary Amine Protonation............................................................................. 83 3
3.5.3.4 Copper Nitrate Trihydrate and Basic Copper Nitrate................................................. 85
3.5.3.5 Conclusions.................................................................................................................. 86
3.6 UV-VIS SPECTROSCOPY .............................................................................................. 88
3.6.1 Ligand Absorption Bands in the UV-Vis Range ......................................................... 88
3.6.2 Copper(II) Complexes Absorption Bands in the UV-Vis Range................................. 88
3.6.3 Conclusions.................................................................................................................. 91
3.7 EPR CHARACTERISATION OF THE COPPER(II) COMPLEXES ........................................ 92
3.7.1 EPR Spectroscopy: Introduction.................................................................................. 92
3.7.2 Spectral Parameters of the Copper(II) Dendromesogens............................................. 95
3.7.2.1 Signal A ........................................................................................................................96
3.7.2.2 Signal B........................................................................................................................ 97
3.7.2.3 Signal C........................................................................................................................ 98
3.7.2.4 Signals D and E ........................................................................................................... 99
3.7.3 Magnetic Properties of the Dendrimeric Copper(II) Complexes: Dimer Formation and
Antiferromagnetism................................................................................................... 102
3.7.3.1 Blue Complexes: Dimeric Structure .......................................................................... 103
3.7.3.2 Green Complexes: Nitrate Bridged Polymeric Structure .......................................... 104
3.7.3.3 Dendrimeric Copper Complex Bridged to a Hexaaquacopper Complex .................. 105
3.7.4 Conclusions................................................................................................................ 107
3.8 THERMAL PROPERTIES............................................................................................... 108
3.8.1 Polarising Microscopy ............................................................................................... 108
3.8.2 Thermal Analysis....................................................................................................... 109
3.8.2.1 Series of Highest Loading: Thermal Properties ........................................................ 111
nd
3.8.2.2 Series of Lower Copper Loading: Thermal Properties of the 2 Generation
Complexes.................................................................................................................. 115
st
3.8.2.3 Series of Lower Copper Loading: Thermal Properties of the 1 Generation
Complexes.................................................................................................................. 119
3.8.2.4 Thermal Properties of the Tetrafluoroborate Copper(II) Complex........................... 112
3.8.2.5 Conclusions................................................................................................................ 123
3.9 X-RAY DIFFRACTOMETRY......................................................................................... 124
ii
3.9.1 Small-angle region..................................................................................................... 125
3.9.1.1 Influence of the Generation on the Mesophase. Series of Highest Loading.............. 133
nd
3.9.1.2 Influence of the Copper Loading on the Mesophase. 2 Generation Complexes of
Different Loadings..................................................................................................... 139
nd
3.9.1.3 X-ray Analysis of the 2 Generation Copper(II) Complex from Tetrafluoroborate
C2.21(4.0).................................................................................................................. 143
3.9.2 Wide-Angle Region................................................................................................... 145
3.9.2.1 Ordered Columnar Mesophases................................................................................ 145
3.9.2.2 Possible Inorganic Impurities in the Dendrimeric Copper(II) Complexes ............... 148
3.9.2.3 Conclusions ............................................................................................................... 153
3.10 PROPOSAL OF A MODEL FOR THE PPI COPPER(II) COMPLEXES ................................ 155
4 SUMMARY ............................................................................................................. 157
5 ZUSAMMENFASSUNG ............................................................................................ 163
6 EXPERIMENTAL SECTION..................................................................................... 169
6.1 MATERIALS................................................................................................................ 169
6.2 ANALYTICAL METHODS ............................................................................................ 170
6.2.1 Molecular Composition Determination: Elemental Analysis, EA............................. 170
6.2.2 Molecular Weight Determination: MALDI-ToF-MS................................................ 170
6.2.3 Spectroscopic Methods.............................................................................................. 171
6.2.3.1 Fourier Transform Infrared Spectroscopy, FTIR...................................................... 171
6.2.3.2 Ultraviolet-Visible Spectroscopy, UV-Vis ................................................................. 171
6.2.3.3 Electron Paramagnetic Resonance Spectroscopy, EPR............................................ 171
6.2.4 Microscopy ................................................................................................................ 172
6.2.4.1 Transmission Electron Microscopy, TEM ................................................................. 172
6.2.4.2 Polarized Light Microscopy, POM............................................................................ 172
6.2.5 Thermal Analysis....................................................................................................... 173
6.2.5.1 Thermogravimetric Analysis, TGA ............................................................................ 173
6.2.5.2 Differential Scanning Calorimetry, DSC................................................................... 173
6.2.5.3 Temperature Dependent X-Ray Diffraction............................................................... 173
6.3 PREPARATIVE METHODS ........................................................................................... 175
6.3.1 Procedures for Copper(II) Nitrate Trihydrate Complexation with PPI Dendrimers.. 175
6.3.1.1 Series of Highest Copper(II) Loading ....................................................................... 175
6.3.1.2 Series of Lower Copper(II) Loading.......................................................................... 178
6.3.2 Procedure for Copper(II) Tetrafluoroborate Hydrate Complexation with
PPI Dendrimers.......................................................................................................... 179
6.4 COMPOUNDS REGISTER I: SYNTHESIS AND CHARACTERIZATION ............................. 180
6.4.1 Dendrimeric Copper(II) Complexes from Cu(NO ) ·3H O....................................... 180 3 2 2
6.4.1.1 Copper(II) Complex of the “Zero” Generation, C0.1(n) .......................................... 180
st
6.4.1.2 Copper(II) Complexes of the 1 Generation, C1.i(n) ................................................ 181
nd
6.4.1.3 Copper(II) Complex of the 2 Generation, C2.i(n)................................................... 183
rd
6.4.1.4 Copper(II) complex of the 3 generation, C3.i(n)..................................................... 193
th
6.4.1.5 Copper(II) Complex of the 4 Generation, C4.i(n) ................................................... 194
th
6.4.1.6 Copper(II) Complex of the 5 Generation, C5.i(n) ................................................... 194
6.4.2 Dendrimeric Copper(II) Complex from Cu(BF ) ·4H O........................................... 195 4 2 2
6.5 COMPOUNDS REGISTER II: X-RAY EVALUATION OF MESOPHASES .......................... 197
iii
6.5.1 Series of Highest Loading: CG.i(n) ........................................................................... 199
6.5.1.1 Columnar Hexagonal Mesophases ............................................................................ 199
6.5.1.2 Columnar Rectangular Mesophases.......................................................................... 200
nd
6.5.2 2 Generation Geries: C2.i(n) ................................................................................... 201
6.5.2.1 Columnar Hexagonal Mesophases ............................................................................ 201
6.5.2.2 Columnar Rectangular Mesophases.......................................................................... 202
st
6.5.3 1 Generation Complexes C1.i(n).............................................................................. 204
6.5.4 Complexes from Cu(BF ) ·4H O............................................................................... 205 4 2 2
7 REFERENCES.........................................................................................................207
ACKNOWLEDGEMENTS
iv

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