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Synthesis of New Tetrazines Functionalized with Photoactive and Electroactive Groups Qing Zhou

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Synthesis of New Tetrazines Functionalized with Photoactive and Electroactive Groups Qing Zhou Synthesis of new tetrazines functionalized with photoactive and electroactive groups Qing Zhou To cite this version: Qing Zhou. Synthesis of new tetrazines functionalized with photoactive and electroactive groups. Other. École normale supérieure de Cachan - ENS Cachan, 2012. English. NNT : 2012DENS0039. tel-00796461 HAL Id: tel-00796461 https://tel.archives-ouvertes.fr/tel-00796461 Submitted on 4 Mar 2013 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. ENSC-(n° dordre) THESE DE DOCTORAT DE LECOLE NORMALE SUPERIEURE DE CACHAN Présentée par QING ZHOU pour obtenir le grade de DOCTEUR DE LECOLE NORMALE SUPERIEURE DE CACHAN Domaine : CHIMIE Sujet de la thèse : Synthesis of new tetrazines functionalized with photoactive and electroactive groups Thèse présentée et soutenue à Cachan le 20/07/2012 devant le jury composé de : Jean-Christophe LACROIX Professeur (Université Paris Diderot) Jean-Manuel RAIMUNDO Maître de conférences (Université Aix-Marseille) Céline FROCHOT Directeur de Recherche CNRS Pierre AUDEBERT Professeur (ENS-CACHAN) Gilles CLAVIER Chargé de recherche CNRS Fan YANG Professeur (ECNU-Shanghai) Fabien MIOMANDRE Maître de conférences (ENS-CACHAN) Jie TANG Professeur (ECNU-Shanghai) Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaire-PPSM ENS CACHAN/CNRS/UMR 8531 61, avenue du Président Wilson, 94235 CACHAN CEDEX (France) Table of Contents Table of Contents .............................................................................................................. 3 Acronyms ........................................................................................................................... 7 General Introduction ....................................................................................................... 9 Chapter 1 Introduction of 1,2,4,5-tetrazine: chemistry and application ............. 13 1.1 Introduction of 1,2,4,5-tetrazine ............................................................................ 13 1.2 Synthesis of s-tetrazines ............................................................................................... 14 1.2.1 Pinner synthesis ........................................................................................ 15 1.2.2 Modification of Pinner synthesis for aliphatic s-tetrazine ........................ 17 1.2.3 Synthesis of dichlorotetrazine .............................................................................. 20 1.3 Reactivity of tetrazine ................................................................................................... 22 1.3.1 Inverse electron-demand Diels-Alder reaction ................................................. 22 1.3.2 Cross-coupling reactions with terminal alkynes .............................................. 26 1.3.3 Aromatic nucleophilic substitution (SNAr reaction) ................................. 28 1.3.4 Azaphilic addition with carbanions ......................................................... 34 1.4 Physical chemistry of s-tetrazine ................................................................................ 36 1.4.1 Electrochemistry of s-tetrazine ................................................................ 36 1.4.1.1 Introduction of electrochemistry ........................................................ 36 1.4.1.2 Electrochemistry of tetrazines ........................................................... 37 1.4.2 Photophysical properties of s-tetrazines .................................................... 40 1.4.2.1 Introduction to photophysical chemistry ............................................ 40 1.4.2.2 Photophysical properties of tetrazines ................................................ 44 1.4.3 Computational chemistry on tetrazines ....................................................... 47 1.5 Applications of s-tetrazines .............................................................................................. 50 1.5.1 Energetic materials from tetrazines ................................................................. 50 1.5.2 Pharmaceuticals from tetrazines ............................................................... 51 1.5.3 Efficient solar cells ................................................................................... 52 1.5.4 NLO-phore with tetrazine ........................................................................ 53 1.6 Conclusions ....................................................................................................................... 54 Chapter 2 New s-tetrazines derivatives as the ion pair receptors ......................... 63 2.1 Introduction ........................................................................................................... 63 2.1.1 Supramolecular chemistry and ion pair receptor .............................................. 63 2.1.2 Fluorescent molecular sensors and electrochemical sensors .......................... 64 2.1.3 Experimental evidence of anion-tetrazine interactions .................................... 66 2.1.4 Anion-p interactions ................................................................................................ 68 2.2 Molecular design of ion pair receptors ...................................................................... 72 2.3 Molecular synthesis ........................................................................................ 77 2.3.1 Preparation of 3,6-dichloro-1,2,4,5-tetrazine ........................................... 77 2.3.2 Preparation of ion-pair receptors ............................................................. 78 2.3.3 Selection and synthesis of ion pairs ......................................................... 79 2.4 Screening for ion-pairs ................................................................................................. 80 2.5 NMR studies of ion pair receptors ............................................................................. 81 2.5.1 1H NMR titration ..................................................................................... 81 2.5.2 Job plot .................................................................................................... 88 2.5.3 Determination of binding constant ........................................................... 89 2.6 Fluorescence studies of ion pair receptors ................................................................ 91 2.6.1 Spectroscopic properties of receptors ....................................................... 91 2.6.2 Titration studies ....................................................................................... 92 2.7 UV-vis absorption studies of ion pair receptors ...................................................... 97 2.8 Conclusions .................................................................................................................. 100 Chapter 3 Studies of tetrazines with bulky or electron withdrawing substituents.107 3.1 Studies of tetrazines with bulky or electron withdrawing substituents ........... 107 3.1.1 Molecular design ................................................................................................... 107 3.1.2 Synthesis .................................................................................................................... 108 3.1.3 Absorption and fluorescence properties ............................................................ 111 3.1.4 Electrochemical properties .................................................................................. 113 3.2 New alkyl-s-tetrazines from an unexpected reaction ........................................... 116 3.2.1 Introduction ............................................................................................................. 116 3.2.2 Optimization and extension of the scope of the reaction ................................. 117 3.2.3 Spectroscopic studies ............................................................................................ 119 3.2.4 Electrochemical studies ........................................................................................ 123 3.3 Toward s-tetrazine based fluorescent dyads ................................................... 125 3.3.1 Molecular design .................................................................................. 125 3.3.2 Synthesis ............................................................................................... 127 3.3.3 Spectroscopic studies ............................................................................ 132 3.3.4 Electrochemical studies ......................................................................... 135 3.4 Tetrazines benzimidazole dyads ............................................................................... 138 3.4.1 Molecular design .................................................................................. 138 3.4.2 Synthesis ............................................................................................... 139 3.4.3 Spectroscopic studies ...........................................................................
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