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Supramolecular Chemistry: from Early Concepts to Supramolecular Polymers

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Supramolecular Chemistry: from Early Concepts to Supramolecular Polymers Macroscopic amplification of nanoscopic motions induced by molecular machines Antoine Goujon To cite this version: Antoine Goujon. Macroscopic amplification of nanoscopic motions induced by molecular machines. Organic chemistry. Université de Strasbourg, 2016. English. NNT : 2016STRAF044. tel-01674231 HAL Id: tel-01674231 https://tel.archives-ouvertes.fr/tel-01674231 Submitted on 2 Jan 2018 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. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. UNIVERSITÉ DE STRASBOURG ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES Institut Charles Sadron THÈSE présentée par : Antoine GOUJON soutenue le : 20 Septembre 2016 pour obtenir le grade de : Docteur de l’université de Strasbourg Discipline/ Spécialité : Chimie Organique et Supramoléculaire Macroscopic Amplification of Nanoscopic Motions Induced by Molecular Machines THÈSE dirigée par : Dr. GIUSEPPONE Nicolas Professeur, Université de Strasbourg RAPPORTEURS : Dr. HASENKNOPF Bernold Professeur, Université Pierre et Marie Curie – Paris 6 Dr. BOUTEILLER Laurent Directeur de Recherche, Université Pierre et Marie Curie – Paris 6 Dr. DE COLA Luisa Professeur, Université de Strasbourg – Présidente du Jury Table of Content Table of content TABLE OF CONTENT.............................................................................................................. 3 ABSTRACT ............................................................................................................................. 7 REMERCIEMENTS ................................................................................................................. 9 ABBREVIATIONS AND SYMBOLS ......................................................................................... 11 RESUME EN FRANÇAIS ....................................................................................................... 13 GENERAL INTRODUCTION AND OBJECTIVES ....................................................................... 27 BIBLIOGRAPHY ................................................................................................................... 31 Chapter I: Supramolecular Chemistry: from early concepts to supramolecular polymers ....................... 33 I. Supramolecular Chemistry ............................................................................................................ 33 II. Supramolecular Polymers ............................................................................................................. 38 A. Definition and examples ........................................................................................................... 38 B. Hydrogen bonding supramolecular polymers .......................................................................... 43 Chapter II: Interlocked molecules and molecular shuttles ...................................................................... 49 I. Interlocked molecules: synthetic strategies, molecular knots and early prototypes of molecular machines 49 A. Molecular topology .................................................................................................................. 49 B. Templated synthesis and increase of complexity ..................................................................... 51 C. Translational isomerism in catenanes: towards molecular shuttles and machines ................. 56 II. Molecular shuttles and molecular muscles: molecular machines in action .................................. 58 A. Molecular shuttles and applications......................................................................................... 58 B. [c2]daisy chains: towards muscle like molecular machines ..................................................... 68 Chapter III: Light-driven rotary molecular motors .................................................................................. 73 I. Rotational molecular motors ........................................................................................................ 73 II. Molecular motors: applications .................................................................................................... 79 General comment on the literature ........................................................................................................ 82 3 Table of Content RESULTS ............................................................................................................................. 83 Chapter IV: Poly[c2]daisy chains based on the 2,6-diacetylaminopyridine and N-hexyluracil recognition motifs ............................................................................................................................................................. 85 I. Objectives and retrosynthesis ....................................................................................................... 85 II. Results ........................................................................................................................................... 88 A. Synthesis of pseudo-rotaxane 12 ............................................................................................. 88 B. Synthesis of bis-N-hexyluracil [c2]daisy chains 1Ext .................................................................. 90 C. Synthesis of bis-uracil linker 3 .................................................................................................. 94 D. Synthesis of bis-2,6-diacetylaminopyridine [c2]daisy chains ................................................... 95 E. Characterization of the contraction/extension event of compound 2Ext ................................. 97 F. Synthesis and characterization of a hydrogen bonding supramolecular polymer ................... 99 G. Imaging of supramolecular polymers 2Ext:3 and 2Cont:3 by TEM and AFM microscopy techniques 102 H. In situ contraction/extension experiments ............................................................................ 106 I. Synthesis of a reticulated supramolecular polymer ............................................................... 107 III. Conclusion ................................................................................................................................... 109 Chapter V: Poly[c2]daisy chains based on the ureidopyrimidinone recognition motif .......................... 111 I. Objectives and retrosynthesis ..................................................................................................... 111 II. Results ......................................................................................................................................... 113 A. Synthesis of protected bis-Upy[c2]daisy chain ....................................................................... 113 B. Characterization of the contraction/extension event of 5Ext .................................................. 117 C. Photo-triggered supramolecular polymerization of 5Ext and 5Cont .......................................... 118 D. Stimuli-responsive behavior of supramolecular polymers 6Ext and 6Cont ................................ 121 E. Characterization of supramolecular polymers 6Ext and 6Cont .................................................. 122 F. Characterization of monomers 5Ext and 5Cont by Small Angle Neutron Scattering (SANS) ...... 125 G. Characterization of supramolecular polymers 6Ext and 6Cont by Small Angle Neutron Scattering (SANS) and Small Angle X-ray Scattering (SAXS) ........................................................................................ 126 III. Conclusion ................................................................................................................................... 129 Chapter VI: Covalent poly[c2]daisy chains and their associated chemical gels ..................................... 131 I. Objectives and retrosynthesis ..................................................................................................... 131 II. Results ......................................................................................................................................... 133 A. Synthesis of covalent polymer 7Ext ......................................................................................... 133 B. Characterization of the contraction/extension event of 7Ext .................................................. 135 C. Characterization of polymers 7Ext and 7Cont by scattering techniques .................................... 137 D. Synthesis of a chemical gel 8Gelx ............................................................................................. 139 E. Stimuli-responsive behavior of gels 8GelxM .............................................................................. 141 4 Table of Content F. Characterization of the contraction/extension event of 8Gel1M by SANS ................................ 144 III. Conclusion ................................................................................................................................... 145 Chapter VII: Dual light control of a contractile gel that integrates molecular motors and modulators subunits ......................................................................................................................................................
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