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

Rhildner

Informations

• Publié par: universitat_bayreuth
• Publié le: 01 janvier 2007
• Nombre de lectures: 33
• Langue: Deutsch
• Poids de l'ouvrage: 15 Mo

Extrait

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...........................