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Research Collection Doctoral Thesis Anthraphanes: a New Class of Potential Monomers for the Synthesis of Two-Dimensional Polymers Author(s): Servalli, Marco Publication Date: 2016 Permanent Link: https://doi.org/10.3929/ethz-a-010832536 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library DISS. ETH NO. 23866 Anthraphanes: a New Class of Potential Monomers for the Synthesis of Two-Dimensional Polymers A thesis submitted to attain the degree of DOCTOR OF SCIENCES of ETH ZURICH (Dr. sc. ETH Zurich) presented by MARCO SERVALLI MSc, ETH Zurich Chemistry born on 10.07.1986 citizen of Bioggio (TI), Switzerland accepted on the recommendation of Prof. Dr. A. Dieter Schlüter, examiner Prof. Dr. Joost VandeVondele, co-examiner Prof. Dr. Peter Walde, co-examiner Dr. Michael Wörle, co-examiner 2016 ACKNOWLEDGEMENTS Acknowledgements Doing a PhD and writing a thesis is not a stand-alone matter and involves the collaboration of many people. I would like to start my acknowledgements from the scientific and work-related point of view: At first, I would like to thank Prof. A. Dieter Schlüter, for offering me the chance to work on the stimulating, fascinating and challenging topic of two-dimensional polymers. Challenging projects deal specially with a lot of frustration and I therefore appreciate the continuous support I received from him during my PhD, in terms of scientific and non-scientific discussion, as well as the essential ongoing motivation to not give up and to keep pursuing my objectives. What I value the most is the large freedom and independence I was given during my work and his critical thinking and meticulous, endorsing attitude when reviewing scientific results. Also, with him I learned the critical importance of diplomacy and communication in academia and science. Further thanks go to my former advisor Prof. Junji Sakamoto. During my PhD’s first year, I worked under his supervision and received constant support. The countless scientific discussions, inputs and clever ideas I received from him, helped my project to advance in the right direction and widened my knowledge and skills in organic chemistry. Prof. Wolfgang Kinzelbach receives my deepest gratitude for helping me in having a smooth and trouble-free transition between my supervisors and for supporting one of my publications. Recurring visits to our group from Prof. Gerhard Wegner and Prof. Benjamin T. King have always resulted in fruitful and enlightening discussions and additional motivation, especially when the project seemed to approach a dead-end. I am very grateful to have made their acquaintance and had the opportunity to witness and assimilate their extensive knowledge. I am very grateful to Prof. Frank-Gerrit Klärner, for his offer to calculate countless electrostatic surface potentials for many of my compounds and sharing his knowledge in the field. I really appreciate his interest in my work and his support for my publications. The main part of this thesis is based on crystallography and has therefore inevitably involved the collaboration of the exceptional crystallography team of the Small Molecule Crystallography Center (SMoCC) at ETH, composed by Dr. Michael Wörle, Dr. Nils Trapp and Michael Solar. I would like to thank Dr. Michael Wörle for his interest in the project, the discussions we had and for the easy access to the synchrotron in Grenoble that he provided; Dr. Nils Trapp solved countless crystal structures for me and struggled to make them publishable when the crystals were not diffracting IV ACKNOWLEDGEMENTS properly. I am also thankful for the countless discussions we had and for proof-reading my thesis and supporting my publications. Finally, I am really indebted with Michael Solar for mounting and measuring countless single crystals and for spending hours in the crystallography lab trying to find properly diffracting samples when needed; I thank him for being patient with me in the times I was a bit pushy. His help in preparing the set-up for the topochemical reactions is also greatly appreciated. I would like to thank Dr. Thomas Weber of the Laboratory of Crystallography for his interest in my work, the discussions we had, for measuring some crystal structures and for the great chance of connecting me with Prof. Hans-Beat Bürgi, who I had the privilege to meet and with whom I could share my results in an enlightening discussion. Many thanks go to Dr. Thomas Schweizer. During my PhD he provided me with a variety of LED- photoreactors and a heating plate with a PID controller for my crystallisation experiments; Also, I would like to thank him for his assistance for any technical-related problem: he repaired countless things and helped me to fix our recycling GPC. We are very lucky to have you in our group! Many thanks go to Prof. Paul Smith for providing access to the light microscopes in his group and to Dr. Kirill Feldman for the kind introduction on the instruments. I would like to thank Prof. Ralph Spolenak and Prof. André Studart for providing access to the AFM and SEM instruments respectively. I am indebted to Dr. René Verel for his kind help with solid-state NMR spectroscopy measurements and any general NMR-related question or problem. Many thanks also go to Doris Sutter for measuring some of my samples on the 500 MHz spectrometer and for the “schoggi-stückeli”. Many thanks go to Rolf Häfliger of the Mass Spectrometry Service at the LOC at ETH for measuring countless of my samples and putting effort into finding the molecular ions peaks when needed. Many thanks also go to Dr. Sara Fornera and Sandra Luginbühl for their help with the fluorescence and UV/Vis absorption spectra in solution. The help of Dr. Alessandro Lauria with the solid-state UV/Vis absorption measurements is greatly acknowledged. I thank Dr. Jingyi Rao for her help with TGA and DSC measurements, Feng Shao for the confocal Raman spectroscopy measurements, Wenyang Dai for the AFM and SEM measurements and Vivian Müller for measuring the UV/Vis absorption and emission spectra of my Langmuir monolayers. V ACKNOWLEDGEMENTS Special thanks go to Dr. Payam Payamyar for his help in anything related to the synthesis of two- dimensional polymers at the air/water interface; I’m really thankful for the introduction to the Langmuir-trough instruments, LEDs, in-situ fluorescence decay measurements both at the air water/interface and with the single crystals, TEM and SEM measurements and general scientific discussions. For scientific discussions on my project I would like to also thank Gregor Hofer, Dr. Max Kory, Bernd Deffner and Prof. Yingjie Zhao. Progress on my project was achieved thanks to the help of students that wished to carry out a semester project with me. In this regard I would like to thank Luzia Gyr, Andri Mani, Nadia Zuurbier and Livius Muff for their essential help in the lab. Special thanks go to my fantastic lab assistant Emmanuel Wirth, who helped a great deal with the synthesis of my key compounds in large scale. Finally, I would like to thank the administrational machine behind our research group, Daniela Zehnder, for taking care of any organisational and administrative matter and Dr. Damir Bozic for all computer-related issues. During my stay in the Schlüter’s group as an undergrad, I have worked in different labs, but I truly felt like home when I landed in G522 at the start of my PhD. The mysterious ability of this lab to gather, attract and keep the most chill and outgoing people resulted not only in a very fruitful working environment and constant mutual support but also in friendships and memorable funny moments with my lab mates: Dr. Thomas Bauer, for all the parties we had together which resulted in cycling in the Limmat, exploring the grounds of the Stuz building, early morning BBQs with top-notch equipment and the memorable trip to Las Vegas, St. Patrick’s Day in NYNY, Area 51 and Spring Break in Lake Havasu with our pilot Matteo and logistic support from Eddie Lane. Other memorable mentions go to Jim, Tyler, Spider and the unbearable Noisy Lady on the plane in Philly. Also, without your foresight, we wouldn’t have taken the plane back to Zurich (but I still think we should have borrowed Jim’s teeth…); Dr. Payam Payamyar, my good friend we had memorable parties and skiing trips together, especially in Boltigen and Gstaad: I’m sorry about that challenging black slope we had to take, but it was really the only way to go to the Ice Bar! On the bright side, the first 300 meters of slope before the cliff were indeed just a narrow flat path as I correctly predicted from the map. I am also thankful for the generous after-party hospitality and dinners at his place, and the countless lunch times we had together at WoKa although after 4 years I still haven’t tried the yellow curry! Ehrlich gesagt, so geht VI ACKNOWLEDGEMENTS das nicht! The time in Japan was epic when “we were feeling perfectly fine, no jet-lagged at all!” and I will never forget the karaoke sessions in Nara and the good food we enjoyed. I am also deeply thankful for the support during the late night fluorescence experiments at FIT. Dr. Ming Li, for letting us visit and shoot an outstanding biographic documentary at his place at 4 am, but especially for his epic google search topics in the lab and the teaching of basic Chinese words; Bernd Deffner, for being part of the aforementioned documentary starring as “The Creature” and afterwards helping me refreshing my ironing skills: now my shirts will always look flawless.