ANNÉE 2017 THÈSE / UNIVERSITÉ DE RENNES 1 sous le sceau de l’Université Bretagne Loire pour le grade de DOCTEUR DE L’UNIVERSITÉ DE RENNES 1 Mention : Chimie Ecole docto rale (Matière, Molécules et Matériaux - 3M) présentée par Jiangk un OUYA NG Préparée dans l’unité de recherche UMR 6226-CNRS-Institut des Sciences Chimiques de Rennes UFR « Sciences et Propriétés de la Matière » (SPM) Thèse sout enue à Rennes Helicenes for Chiral le 13 décembre 2017 devant le jury composé de : Dr Federic o CISNETTI Molecular S wi tches, Maître de Conférences, Université Clermont Auvergne/ Rapporteur Magnetic Ma terial s, Dr Eric MANOURY Directeur de recherche CNRS, LCC Toulouse/ Rapporteur and Chiral Full erene Dr Narcis AVARVARI Directeur de recherche CNRS, Moltech Anjou/ Examinateur Deriv atives Dr Joëlle RAULT-BERTHELOT Directeur de recherche CNRS, ISCR/Examinateur Dr Patric k ROSA Chargé de recherche CNRS, LCC Bordeaux/ Examinateur Dr Jeanne CRASSOUS Directeur de recherche CNRS, ISCR/ Directeur de thèse Dr Ludo vic FAVEREAU Chargé de recherche CNRS, ISCR/Membre invité For My Dear Mother “Jinlian ZHANG” For My Dear Father “Chengsheng YANG” For My Dear Grandmother “Chunxiu ZHANG” For My Dear Sister “Senli YANG” For My Brother-in-Law “Rong DENG” For My Niece “Yarui DENG” and Nephew “Haochen DENG” “Whatever is worth doing is worth doing well!” Lewis CARROLL 1 Pour ma vie compagnon dans le futur “Si tu aimes une fleur qui se trouve dans une étoile, c'est doux, la nuit, de regarder le ciel. Toutes les étoiles sont fleuries.” Antoine de SAINT-EXUPERY «Le Petit Prince» 2 Acknowledgements How time flies! I can still remember the first day I arrived at the lab three years ago. Now I will finish my PhD study. Firstly, I would like to send my sincerest gratitude to my supervisor Dr. Jeanne CRASSOUS for her kindness, patience, enthusiasm, and abundant knowledge. I will never forget that she accepted me and provided me the opportunity to study my PhD in her group three years ago. During these three years, she taught me not only the chemistry and experiment, but also how to do research and a good presentation and write a thesis. Especially, she spent a lot of time in correcting my thesis. I would especially like to thank my thesis committee whom I appreciate for accepting to referee my thesis: Dr. Federico CISNETTI, Dr. Eric MANOURY, Dr. Narcis AVARVARI, Dr. Joëlle RAULT-BERTHELOT, Dr. Patrick ROSA, Dr. Ludovic FAVEREAU. I would thank all the collaborators, Dr. Fabrice POINTILLART, Dr. Boris Le GUENNIC, Prof. Olivier CADOR, Prof. Nazario MARTIN, Prof. Salvatore FILIPPONE, Prof. Rudolf PIETSCHNIG, Dr. Christophe LESCOP, Dr. Nicolas VANTHUYNE (Chiral HPLC separation), Dr. Thierry ROISNEL and Dr. Vincent DORCET (X-Ray crystallography), Rosa M. GIRON, and Sebastian HARTUNG. I would also thank Dr. Ludovic FAVEREAU for teaching me chemistry knowledge and experiment technique. Equally, thank to Prof. Muriel HISSLER and Dr. Pierre-Antione BOUIT for their kind help in the lab. My sincere thanks also go to Thibault REYNALDO for his help in ordering chemical compounds and solving technique problems, and to Cecile PERON who was always available to help me to deal with things about traveling and conference. Many thanks to Dr. Chengshuo SHEN for his huge help at the beginning of my PhD study. Thanks to Dr. Helena ISLA MATA for teaching me experiment skills. I greatly appreciate to Dr. Nora HELLOU for sharing the same lab and helping me. Thanks to Dr. Nidal SALEH for that I continued part of his work. I would also thank all my dear labmates in PMM group: Dr. Matthew DUFFY, Anabella MOCANU, Kais DHBAIBI, Jonas HOFFMANN, Thomas DELOUCHE, Etienne GAUTHIER, Nesrine HAFEDH, Sondes RAOUAFI, Dr. Thomas DOMBRAY, Dr. Faouzi CHAHDOURA, Dr. Antoine MAUFROY, Dr. Thomas MALNOE, Dr. Sloane EVARISTE, Dr. Nicolas de RYCKE, Dr. Tereza VITVAROVA, Dr. Rozsa SZUCS, 3 Réka MOKRAI. It is really happy to meet you in the lab during my PhD study. I wish you all the best in the future. I am grateful to Prof. Pierre-Henri DIXNEUF for inviting me to drink wine and driving me back. I wish to thank Prof. Christophe DARCEL, Prof. Henri DOUCET, and Dr. Jean-Baptiste SORTAIS for their interesting catalysis lessons. Many thanks to my neighbour lab for providing me convenience for UV-vis measurement. I would like to thank my friends Changsheng WANG, Shengdong WANG, Feng YU, Duo WEI, Yuchao YUAN, Xinzhe SHI, Haoran LI, Haiyun HUANG, Zhuang ZHANG， Yixuan CAO, Weiheng HUANG, Shuxin MAO, Yaoyin LOU, Guangxing LIANG, Yanghai XU, Kedong YUAN, Xiaoyan HE, Le YU, Min FENG, Wenyan HE, Xiaolu MA, Ding WANG, Jingran HOU, Rui SANG, Yuya HU, Shi JIANG, Mian HE, Xiang LIU. Finally, I would like to express my greatest appreciation to my family. My parents always supported and encouraged me during my PhD. They are my strong backing. Many thanks to my grandmother who raised me up also gave me encouragement. I hope she will always be healthy. I genuinely thank and appreciate my older sister and brother-in-law for helping me to take care of my parents and grandmother when I studied abroad. Thanks to my lovely niece and nephew for bringing me so much happiness. Jiangkun OUYANG 31.10.2017 4 Abbreviations Å: Angstrom OLEDs: Organic light emitting diodes BINOL: 2,2'-dihydroxy-1,1'-binaphthyl OR: Optical Rotation BuLi: Butyl Lithium Rac: racemic CD: Circular Dichroism RISC: Reverse intersystem crossing CIP: Cahn-lngold-Prelog ROESY: Rotating frame overhause effect spectroscopy CPL: Circular Polarized Luminescence R.T: Room Temperature CP-PLED: circular polarized phosphorescence light emitting diode RRM：reaction on racemic mixture DCC: dicyclohexyl carodiimide SAM: self- assembled monolayer DMPC: 1,2-dimyristoyl-sn-glycero-3- SIMs: single-ion magnets phosphorylcholine SMMs: Single molecule magnets DTE：dithienylethene SOC: Spin-orbital coupling ECD: Electronic circular dichroism SQUID: Superconducting Quantum Interference ee: enantiomeric excess Device hfac: 1,1,1,5,5,5-hexafluoroacetonate anion TADF: Thermally activated delayed fluorescence HPLC: Hihg-Performance Liquid Tc: curie temperature Chromatography TN: Neel temperature HOMO: Highest occupied molecular orbital TB: blocked temperature HRMS: High resolution mass spectrometry THF: Tetrahydrofuran ISC: Intersystem crossing TMSA：trimethylsilylacetylene ILT: intra-ligand transition UV-vis: Ultraviolat-visible LSVs: linear sweep voltammograms UPy: 2-ureido-4[1H]-pyrimidinone LLCT: Ligand-to-ligand charge transfer Ueff: effective energy barrier LEECs: Light emitting electrochemical cells Φ: Quantum yield LMCT: ligand-to-metal charge transfer transitions ω: angular frequency 23 LUMO: Lowest unoccupied molecular orbital [훼]퐷 : Specific optical rotation 23 MCT: metal centered transitions [∅]퐷 : Molar optical rotation MLCT: Metal-to-ligand charge transfer ε: Molar absorption coefficient NMR: Nuclear Magnetic Resonance χm: magnetic susceptibility 5 6 Table of Contents Chapter I General introduction: helicenes and applications .................................................. 11 A General introduction .............................................................................................................. 11 A.1 Chirality .......................................................................................................................... 11 A.2 Helicenes ........................................................................................................................ 14 B Conclusion ............................................................................................................................. 30 C References .............................................................................................................................. 31 Chapter II Photoresponsive chiral switches based on helicenes and gold complexes .......... 32 A General introduction: design of the project ........................................................................... 35 A.1 Photoresponsive chiral switches based on helicenes ...................................................... 35 A.2 Photoresponsive gold complexes .................................................................................... 36 B Stiff stilbenes substituted with helicenes ............................................................................... 37 B.1 Bibliographic part ........................................................................................................... 37 B.2 Stiff stilbenes .................................................................................................................. 38 B.3 Photoisomerization mechanism of stiff stilbene ............................................................. 38 B.4 Applications of stiff stilbene ........................................................................................... 40 B.5 Introduction of helicenes in light-driven chiroptical switches. ....................................... 46 B.6 Results and discussion .................................................................................................... 50 B.7 Coordination tests ........................................................................................................... 63 B.8 Conclusion ...................................................................................................................... 64 C Stiff stilbenes substituted with alkynyl-gold units ................................................................. 65 C.1 Generalities on gold(I) complexes .................................................................................