S412 Molecular complexes SACL 9 for artificial photosynthesis : 201 Thèse de doctorat de l'Université Paris-Saclay NNT préparée à Université Paris Sud École doctorale n°571 Sciences chimiques : molécules, matérieux, instrumentation et biosystèmes (2MIB) Spécialité de doctorat: Chimie Thèse présentée et soutenue à Orsay, le 6 novembre 2019, par Mme Youngju RO Composition du Jury : Pierre MIALANE Professeur, Université Versailles Saint-Quentin-en-Yvelines Président Sébastien RICHETER Maître de Conférences - HDR, Université de Montpellier Rapporteur Yann PELLEGRIN Directeur de Recherches, Université de Nantes Rapporteur Eric DORIS Chercheur de CEA, CEA Saclay Examinateur Charles DEVILLERS Maître de Conférences - HDR, Université de Bourgogne Examinateur Ally AUKAULOO Professeur, Université Paris Sud Directeur de thèse Université Paris-Saclay Espace Technologique / Immeuble Discovery Route de l’Orme aux Merisiers RD 128 / 91190 Saint-Aubin, France 4 Acknowledgement I appreciate Prof. Ally Aukauloo for giving me an opportunity to work in Laboratoire de Chimie Inorganique. I remember the moment when I met him first time. He convinced me to go ahead for the research to focus on science. The most memorable sentence which he told me is “I will take the challenge.”. With his impact decision, all situations flowed naturally, and I also reacted to produce fruitful output. I really liked to discuss with him whenever I had curiosity and questions in any kinds of topic. It had always been my strong motivation to go through the meaningful road. Especially, I could learn about Artificial Photosynthesis by approaching various points of view. Thank you for being my supervisor. I would like to thank Dr. Winfried Leibl. He is my great advisor both in research and life. If someone ask me ‘express him in some words’, without hesitating, I would say ‘wisdom and warmness’, which I like most. We often shared the research idea, tried and finally succeed. Among his teaching for me, mainly I learned photophysics and understood the principle of photocatalysis. I am thankful to Dr. Zakaria Halime. I was impressed with his passion toward the research. I could learn a lot from the beginning to the end! How to synthesis, characterize metal complexes, control the parameter to make crystal, and work in glove box….all about chemistry! When I asked about science, anytime he opened his heart and he spent time for me. Especially, I will miss his joking which makes me fun during working. I thanks to Dr. Marie Sircoglou. She took care of my safe and security so I could be careful about my experiment. For the ion pair study, her comments helped me to approach in depth. Thank you Dr. Annamaria Quaranta. When I used instruments in CEA, she helped me a lot. I was happy when you commented to me for my presentation during weekly seminar. I liked the environment which we could discuss freely. 5 Many thanks to Dr. Christian Herrero for EPR measurements. I would like to thank Dr. Régis for analysis crystals. Also, lots of thanks to Dr. Eric for the magnetism measurements. You all explained the data analysis carefully and always you welcome me! I appreciate to Dr. Sébastien Richeter and Dr. Yann Pellegrin who accepted the task of being reporters of my defense. They reviewed my thesis report and commented to support the results. Furthermore, I would like to thank Prof. Pierre Mialane, Dr. Eric Doris, and Dr. Charles Devilliers for examining my thesis. I always try to find for diverse challenging & rewarding higher education and the SERP-Chem which was my master program in Europe made it possible for me which I am always thankful for. Above all, I thanks to Prof. Sandrine Lacombe who is the director of the SERP-Chem Program, she listened to me always and suggest better way for me not only during master but also during my Ph.D. I appreciate to people in Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO) at Université Paris-Sud, Institut de biologie intégrative de la cellule (I2BC) at CEA Saclay. In addition, thanks to École doctorale for the financial supporting during my Ph.D. Last but not the least, I am always thankful to my family members. My study in Europe was fully supported by your love and pray! Jin Choi, my husband since my master in 2014, thanks for his following to cheer me up throughout my Ph.D degree have been memorable. Especially my lovely babies (puppies) Sun & Moon, you are my sunshine and moonlight during day and night. Let’s make new road for the bright future together to be happy. 6 7 8 The goal is not to be perfect by the end. The goal is to be better today. Simon Sinek 9 10 Table of contents Acknowledgement ........................................................................................................................................ 5 Table of contents ........................................................................................................................................ 11 Abbreviations .............................................................................................................................................. 15 0. Thesis Overview ................................................................................................................................... 19 1. General Introduction ........................................................................................................................... 23 1.1. Artificial Photosynthesis ............................................................................................................. 23 1.1.1. From biological to artificial photosynthesis ........................................................................ 23 1.1.2. Global Warming crisis and Solar Energy ............................................................................. 25 1.1.3. Photosystem II : Oxygen Evolving Center and Water Splitting ........................................... 27 1.2. Photoinduced activation of water .............................................................................................. 28 1.2.1. Water Oxidation, O2 evolution ............................................................................................ 28 1.2.2. Ruthenium-based Photosensitizers .................................................................................... 33 1.2.3. Study of Water Oxidation using Copper Catalysts .............................................................. 35 1.3. Ion Pair Formation ...................................................................................................................... 38 2. Electrochemical Water Oxidation ....................................................................................................... 43 2.1. Introduction ................................................................................................................................ 43 2.2. Experimental methods ................................................................................................................ 48 2.2.1. Synthesis of Copper complex .............................................................................................. 48 2.2.2. Electron acceptors .............................................................................................................. 48 2.3. Characterizations of CuIIOPBI ...................................................................................................... 52 2.3.1. Cyclic Voltammetry (CV) ..................................................................................................... 52 2.4. Electrochemical water oxidation ................................................................................................ 54 2.5. EPR spectro-electrochemical experiments ................................................................................. 58 2.6. Other Copper complex, CuIIOBBZ................................................................................................ 64 2.6.1. CV of CuIIOBBZ ..................................................................................................................... 65 2.6.2. Electrochemical water oxidation by CuIIOBBZ .................................................................... 66 2.7. Photochemical water oxidation .................................................................................................. 71 2+ 2.7.1. Photophysical studies between [Ru(bpy)3] and Copper complex .................................... 71 2.7.2. Oxygen measurement by Clark Electrode ........................................................................... 73 2.8. Conclusions & Perspectives ........................................................................................................ 75 11 3. Ion pair formation ............................................................................................................................... 79 3.1. Introduction ................................................................................................................................ 79 3.2. Synthesis and Characterizations ................................................................................................. 83 3.2.1. Synthesis ............................................................................................................................. 83 3.2.2. Characterizations ................................................................................................................ 84 A) 1H NMR analysis of Ligand .............................................................................................................