Supramolecular photochemistry of ruthenium(II) oligopyridine complexes

Supramolecular photochemistry of ruthenium(II) oligopyridine complexes

Table of Contents

Chapter I: Introduction to supramolecular photochemistry…………………………..............13

I. Supramolecular photochemistry………   .….......14

·       Introduction……………………………….............14

·       Supramolecular species……………………......16-18

·       Photochemical and photophysical proces….......19-25

·       [Ru(bpy)₃]²⁺…………      ……………….... .....26-28

·       Cage-type systems……………..................... ......29-31

·       Host-Guest systems…………..............................32-34

II. Supramolecular systems using Ru(II)-polypyridine complexes...………………….…….........................................35

·Supramolecular.self.assembly.machines………......35-45

·       Rotaxanes-Molecular  Shuttles...................................46-54

·       Covalently-linked molecular components……..........55-56

·       Dendrimers……………………………………..........57-61

·       Metallosupramolecular chemistry…………………………………................62-63

·      References………………………………...................64-67

Chapter II: Synthesis of ruthenium (II) complexes of 4,4'-bis(phenyl)-2,2'-bipyridine ligands....................76

·       Introduction…………………………………….77-78

·       Synthesis of 4,4'-bis(4-methoxyphenyl)-2,2'-bipyridine 7, and 4,4'-bis(3,5-dimethoxyphenyl)-2,2'-bipyridine 10...............................................................................79-81

·       Synthesis        of    4,4'-dibromo-2,2' bipyridine…………………......................................82-83

·       Synthesis of 4,4'-bis-(4-methoxyphenyl)-2,2'-bipyridine 7…...........................................................................84-87

·       Synthesis of 4,4'-bis-(1-naphtyl)-2,2'-bipyridine 13…….................................................................…88-89

·       Synthesis of [Ru(bpy)2(7)] [PF6]2 and [Ru(bpy)2(10)] [PF6]2..................................................................... 90-99

·       Conclusion and perspectives………..............................100

·       Experimental section…………...............................101-105

·       References…………………………………….......106-107

Chapter III: Synthesis of ruthenium (II) complexes of 4´-phenylsubstitued-2,2´:6´,2´´-

terpyridine complexes……………………………….108

·       Introduction………………………………………109-110

·       Synthesis of 4-substitued-2,2´:6´,2´´-terpyridine ruthenium(II) complexes……................................111-116

·       Synthesis of Y Shaped ruthenium complex............117-122

·       Synthesis of Dendron B 46…………...…………..123-131

·       Conclusion…………………………………………......132

·       Experimental procedures……………….................133-140

·       References………………………………………...........141

Chapter IV: Photophysical and electrochemical investigations of the 4-methoxy and 3,5- dimethoxyphenyl substituted ruthenium(II) oligopyridine complexes…………………..................142

·       Introduction…………………………………….....143-144

·       Theoretical aspects of the metal-to-ligand charge tranfert (MLCT)……………………...................................145-150

·       Electrochemistry......................................................151-153

·       Conclusion and Discussion.............................................154

·       References……………………………………...............155

Chapter V: Synthesis and photochemical investigation of 4,4´-bis(3,5-dimethoxyphenyl)- 6,6´-dimethyl-2,2´-bipyridine copper(I) and ruthenium(II) complexes……………….........................156

·       Introduction………………………………….............157

·       II. Synthesis of 4,4´-bis(3,5-dimethoxyphenyl)-6,6´-dimethyl-2,2´-bipyridine copper(I) complex 59...........................................................................158-161

·       Synthesis of [Ru(bpy)₂(58)][PF₆] complex 60..............162

·       Photophysical and electrochemical properties of complexes …………………............................................................163

·       Photophysical & Electrochemical properties if complexes.......................................................................163

·       Conclusion………………………………………...........163

·       Experimental section………………………............164-166

·       References……………………………………….......….167

Chapter VI: From pyrene to polymetallic dyads...168

·       Introduction………………………………......................169

·       Wire type polyads………………………….............170-172

·       The pyrene excimer theory…………………….......173-176

·       Synthesis of 1-pyrenyl Ru , Os and Ir complexes............177

·       Photophysical and electrochemical properties of the 4-pyrenyl-2,2´:6´, 2´´-terpyridinecomplexes...............178-182

·       Electrochemical investigations…………………………183

·       Conclusion………………………………………...........183

·       Experimental section……………………………....184-188

·       References……………………………………................189

Chapter VII: Synthesis of narrow band gap spacers using non-classical pelectron ring  systems..............190

·       Introduction……………………………………………191

·       Organic p-conjugated systems………………………………………....…192-193

·       Synthesis of 4,7 diethynyltrimethylsilylbenzo[c][1,2,5]thiadiazole 75…..........................................................................194-196

·       Synthesis of 6,13-pentacene derivates………………………………….......….....194-198

·       Conclusion………………………………………….......199

·       Experimental section................................................200-204

·       References………………………................………204-206