MANGANESE/LANTHANIDE HETEROMETALLIC CAGE CHEMISTRY: A MOLECULAR APPROACH TO PEROVSKITE MANGANITES By DAISUKE TAKAHASHI A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2019 © 2019 Daisuke Takahashi To everyone who has supported me ACKNOWLEDGMENTS Before I begin, I would like to note that it has been quite a while since I wrote acknowledgments on such a formal occasion last time that I do not remember if there is any particular rule that I am supposed to follow in order not to be unintentionally rude to any of those who are acknowledged herein. The Guide for Preparing Theses and Dissertations created by the University of Florida Graduate School does not clearly specify how acknowledgments need to be tailored and especially in what order the people who helped should be mentioned, therefore I decided to write in chronological order, which I think will minimize the possibility of failing to cover all the important names by accident. First of all, I would like to thank my family, especially my parents, for their continuous support and sacrificial love since the day I was born. My mother has been very enthusiastic about my education; she had already sent me to a cram school even before I began formal education in elementary school at the age of six, which is as far back as I can remember. While caring for her parents at home twenty-four hours a day, seven days a week, she was always willing to drive me to and from school and prepared a fantastic dinner every night, which I had never been able to fully appreciate until I started living by myself in the United States. She has always encouraged me to learn new things, for which she never hesitated to pay money. She made sure that I was able to get the best education and nurture my curiosity about whatever I feel interested in, which I firmly believe has moulded me into what I am. My father, on the other hand, did not look serious about education and never told me to do the homework or study hard. As he himself has been a scientist for a long time, he might have wanted me to understand the importance of studying and learning on my own initiative rather than being told to do so. However, it does not mean that he was not an enthusiastic supporter of me; when I was in a research group in the University of Tokyo, I had to work so hard every day that I missed the last train countless times. 4 For such occasions, he always drove a long way from home to pick me up late at night so that I could take a shower, sleep in bed even just for a little time, and have decent breakfast in the following morning. Since the day I was born, I have lived with the maternal grandparents, and their unconditional love never ceased to amaze me. My maternal grandmother suffered from a cerebral hemorrhage when I was at the age of eight and has been bedridden since then, but is still so full of energy in the mid 80s that she actually learned how to use a smartphone after I moved to the U.S., and send me an email frequently to make sure I am okay far away from home. My maternal grandfather has dementia and can no longer recognize me very well, but he used to be a kendo (Japan’s traditional martial arts that resemble fencing) master and we shared a passion for professional wrestling when I was a junior high and high school student. My paternal grandfather passed away from cancer almost twenty years ago, but his strong personality influenced me so greatly that his memory never fades away. My paternal grandmother is a very talented artist still active at the age of almost 90, and whenever I visit her in my father’s home in Noto, Ishikawa, she teaches me a lot of things from paintings and drawings to pottery making and ikebana (flower arrangement). My father has one older sister and one younger brother; my aunt Chie runs a small wine bar/restaurant with her husband in Nanao, Ishikawa, facing beautiful Toyama Bay, and their relaxed lifestyle has greatly inspired me. My uncle Takayuki has been working in many international pharmaceutical companies after he got his Ph.D. degree in Hawaii. He was the person who understood my passion for studying overseas the most and encouraged me to take a risk and make a big decision. Family members are not necessarily limited to humans but also include pets; I started living with Burger, a Beagle, soon after I had entered the elementary school, and grew up 5 together for thirteen years until the day he died when I was a third-year college student. His formal name was Harvey Slumfenburger, which had been named after the name of a boy in my favorite picture book by John Burningham, “Harvey Slumfenburger’s Christmas Present”. He was such a naughty boy that he kept stealing vegetables from our neighbor’s field and picking through garbage at dump sites, and finally developed a feud against crows who thought Burger was trying to grab their territory. On one occasion, he had suddently bitten a hole through the trouser of a passerby, who turned out to be a member of the ward assembly. Instead of compensating for damage, we had to put up an election campaign poster of his political party on a wall in front of my house every time there was an election. When I started to study chemistry, I wished I would be able to discover a new element so I could name it after Burger (Burgerium, perhaps?), which I thought would be a great gift for him. In “Harvey Slumfenburger’s Christmas Present”, Father Christmas had found in his sack one present left, which was for a small boy called Harvey Slumfenburger, who lives far away on top of the Roly Poly Mountain, and so he went on a journey to deliver the present to him before Christmas comes. Since the day Burger died, I have been feeling in the same way as Father Christmas; I have to keep going how hard my life becomes and when I finish the journey of life and reunite with him on top of the Roly Poly Mountain, I can finally deliver him a gift, which is how I live splendidly with his spirit together. I really hope he will like it. Secondly, I would like to thank my teachers and friends I met during my elementary school days. Studies in Shukutoku elementary school were quite competitive as every student scrambled to pass an entrance exam and get into a better junior high school, however, it was not very stressful for me because I loved studying very much; I was not interested in reading comic books, watching anime, playing video games, or enjoying sports as many others preferred over 6 studying. What made me stressed out were all the detailed rules about what to do and what not to do. Shukutoku was established based upon a specific type of Buddhist philosophies and practice called Mahayana, and everyday activities involved prayers before the first class begins and after the last class ends, which I thought a waste of time. Although many of the teachers seemed to me more interested in finding violations in the personal hygiene or the grooming standard than academic teaching, there were a few teachers who were different. I greatly appreciate Mr. Mikiya Sugawara and Mr. Shinichi Yamanouchi, a chemistry teacher and a mathematics teacher, respectively, for their true passion for academic studies; their classes cultivated my genuine curiosity about science. I am also truly thankful for Ms. Yoshie Mishima, who was my homeroom teacher for four years. She must have been annoyed very much at my very poor grooming, but never gave up on me. She was one of very few teachers that I have met in my life who treated students very fairly and equally, and tried to develop their merits instead of suffocating individuality. I would also like to thank Naoto Aoki Yatake, the best and oldest friend of mine, for everything he has shared with me: our love and passion for soccer, Japanese folk music, and professional wrestling, and above all a strong, enduring friendship that still stands the test of time and allows us to call each other comrade. Thirdly, I would like to thank my teachers and friends I met in Musashi Junior and Senior High School. Founded in 1922 as Japan's first-ever seven-year secondary boys' school, the school has always emphasized the Three Founding Principles as its perpetual spirit of education: (i) To produce individuals dedicated to our nation's ideal of incorporating the cultural values of East and West; (ii) to produce individuals equal to the challenge of acting on the world stage; and (iii) to produce individuals capable of independent thought and research, all of which have become my flesh and blood. The first principle can be regarded as the very antithesis of the 7 Japan’s past nationalism, which triggered the World War II and led the world as well as ourselves to catastrophe, and talks about the importance of understanding different cultural values. The second principle sounds even more relevant in the current trends of globalization as it emphasizes the need of acquiring the knowledge and power to be able to make the world one’s stage, which along with the first principle strongly motivated me to go out of my home country and pursue the Ph.D.