Supramolecular polymers of triarylamines : studies in aqueous medium and covalent capture of their self-assemblies Ting Liang To cite this version: Ting Liang. Supramolecular polymers of triarylamines : studies in aqueous medium and covalent capture of their self-assemblies. Organic chemistry. Université de Strasbourg, 2017. English. NNT : 2017STRAF044. tel-02003365 HAL Id: tel-02003365 https://tel.archives-ouvertes.fr/tel-02003365 Submitted on 1 Feb 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. 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INSTITUT CHARLES SADRON UNIVERSITÉ DE STRASBOURG THÈSE présentée pour obtenir le grade de DOCTEUR de l’UNIVERSITÉ DE STRASBOURG par Ting LIANG Supramolecular Polymers of Triarylamines: Studies in Aqueous Medium and Covalent Capture of Their Self-assemblies Soutenue publiquement le 13 janvier 2017 devant le jury composé de: Docteur Olivier Colombani (SRSMC UMR 7565, Le Mans) – Rapporteur externe Professeur Patrice Woisel (CNRS UMR 8207-Universite Lille 1) – Rapporteur externe Professeur Nicolas Giuseppone (ICS, Université de Strasbourg – CNRS, Strasbourg) – Directeur de thèse Docteur Emilie Moulin (ICS– CNRS, Strasbourg) – Co-directeur de thèse Discipline : chimie organique Table of Contents ABSTRACT ........................................................................................................................................................ 3 RÉSUMÉ EN FRANÇAIS...................................................................................................................................... 5 ACKNOWLEDGEMENTS................................................................................................................................... 15 ABBREVIATIONS AND SYMBOLS ..................................................................................................................... 17 GENERAL INTRODUCTION AND OBJECTIVES ................................................................................................... 19 BIBLIOGRAPHICAL PART ................................................................................................................................. 21 CHAPTER I: GENERALITIES ON SUPRAMOLECULAR POLYMERS ......................................................................................... 23 1. Supramolecular polymers .......................................................................................................................... 23 a. Definitions ..................................................................................................................................... 23 b. Examples ....................................................................................................................................... 27 2. Characterizations of supramolecular polymers ......................................................................................... 31 3. Applications of supramolecular polymers ................................................................................................. 35 a. Self-healing materials .................................................................................................................... 35 b. Optoelectronic materials ............................................................................................................... 37 c. Biomedical applications ................................................................................................................. 39 d. Supramolecular catalysis ............................................................................................................... 41 CHAPTER II: SUPRAMOLECULAR POLYMERS IN AQUEOUS MEDIUM .................................................................................. 43 1. Hydrogen bonding supramolecular amphiphiles ....................................................................................... 43 2. π-π stacking supramolecular amphiphiles ................................................................................................. 46 3. Supramolecular amphiphiles based on host-guest interactions ................................................................ 50 4. Supramolecular amphiphilic polymers controlled by electrostatic interactions ....................................... 54 CHAPTER III: CROSS-LINKED SUPRAMOLECULAR POLYMERS ........................................................................................... 57 1. Cross-linked polymers built from ring opening metathesis polymerization (ROMP) ................................ 57 2. Cross-linked supramolecular polymers built from sol-gel processes ......................................................... 62 3. Other methods to reach cross-linked supramolecular polymers .............................................................. 66 CHAPTER IV: SUPRAMOLECULAR POLYMERS BASED ON TRIARYLAMINES ........................................................................... 71 RESULTS.......................................................................................................................................................... 81 CHAPTER V: WATER-SOLUBLE SUPRAMOLECULAR POLYMERS BASED ON TRIARYLAMINE MOTIFS ........................................... 83 1. Objectives and targeted molecules ........................................................................................................... 83 2. Synthesis and characterization of triarylamine-polyethylene glycol derivative ........................................ 84 a. Synthesis ........................................................................................................................................ 84 b. Characterizations .......................................................................................................................... 85 c. Discussion ...................................................................................................................................... 90 3. Synthesis and characterization of triarylamine-peptide derivative ........................................................... 91 a. Synthesis ........................................................................................................................................ 91 b. Characterizations .......................................................................................................................... 93 c. Discussion .................................................................................................................................... 101 4. Synthesis and characterization of triarylamine-Cy3 derivative ............................................................... 101 a. Synthesis ...................................................................................................................................... 101 b. Characterizations ........................................................................................................................ 103 c. Discussion .................................................................................................................................... 108 5. Conclusions .............................................................................................................................................. 109 CHAPTER VI: CROSS-LINKED SUPRAMOLECULAR POLYMERS BASED ON TRIARYLAMINE MOTIFS ............................................ 111 1. Objectives and targeted molecules ......................................................................................................... 111 2. Synthesis .................................................................................................................................................. 112 a. Synthesis of triarylamine-urea-siloxane derivative ...................................................................... 112 b. Synthesis of triarylamine-amide-siloxane derivative ................................................................... 112 c. Synthesis of triarylamine-norbornene derivative ........................................................................ 114 3. Characterizations ..................................................................................................................................... 114 a. Characterizations of Gel-TEOS1 and Gel-TAEOS2 ........................................................................ 114 b. Characterizations of Gel-TANBE .................................................................................................. 119 4. Conclusions .............................................................................................................................................. 133 CONCLUSIONS AND PERSPECTIVES ............................................................................................................... 135 EXPERIMENTAL PART .................................................................................................................................... 137 1. General procedures ................................................................................................................................