Polymerization Control in Surface-Mounted Metal-Organic Frameworks Zur Erlangung des akademischen Grades einer DOKTORIN DER NATURWISSENSCHAFTEN (Dr. rer. nat.) von der KIT-Fakultät für Chemie und Biowissenschaften des Karlsruher Instituts für Technologie (KIT) genehmigte DISSERTATION von M. Sc. Beren Sen aus Istanbul, Türkei 1. Referent: Prof. Dr. Christof Wöll 2. Referent: Prof. Dr. Stefan Bräse Tag der mündlichen Prüfung: 07.12.2020 This document is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License (CC BY-SA 4.0): https://creativecommons.org/licenses/by-sa/4.0/deed.en The present thesis was carried out from March, 2017 to June, 2020 under the supervision of Prof. Dr. Christof Wöll at the Institute of Functional Interfaces (IFG) in Karlsruhe Institute of Technology (KIT). I hereby declare that this Ph.D. thesis is based on my work and it was written solely by myself. I did not use any other sources, references and aids other than those mentioned in the thesis. All the text and figures that are not my own cited properly by me. Beren Sen Karlsruhe, 16.12.2020 TABLE OF CONTENTS ABSTRACT ..................................................................................................................................... i ZUSAMMENFASSUNG .............................................................................................................. iii 1. INTRODUCTION ..................................................................................................................... 1 1.1 Metal-Organic Frameworks .................................................................................................... 1 1.2 Surface-Mounted Metal-Organic Frameworks ....................................................................... 3 1.2.1 Substrates and surface functionalization of SURMOFs .................................................. 4 1.2.2 Liquid phase epitaxy ........................................................................................................ 5 1.2.3 Preparation methods of SURMOFs ................................................................................. 7 1.2.3.1 Spray method ............................................................................................................ 7 1.2.3.2 Pump method ............................................................................................................ 8 1.3 Polymerization in MOFs ........................................................................................................ 9 2. THEORETICAL BACKGROUND OF THE CHARACTERIZATION TECHNIQUES. ................................................................................................................................................... 13 2.1 X-Ray Diffraction ................................................................................................................. 13 2.2 Infrared Spectroscopy ........................................................................................................... 15 2.3 Raman Spectroscopy ............................................................................................................ 19 2.4 Ultraviolet-Visible Spectroscopy ......................................................................................... 20 2.5 Mass Spectrometry ............................................................................................................... 22 2.5.1 Matrix-assisted laser desorption ionization time of flight mass spectrometry .............. 22 2.5.2 Time-of-flight secondary ion mass spectrometry .......................................................... 23 2.6 Scanning Electron Microscope and Energy Dispersive X-Ray Analysis ............................. 24 3. EXPERIMENTAL SECTION ................................................................................................ 27 3.1 Materials ............................................................................................................................... 27 3.2 Functionalization of Substrates ............................................................................................ 27 3.2.1 Gold substrates ............................................................................................................... 27 3.2.2 Silicon substrates ........................................................................................................... 28 3.2.3 Quartz substrates ............................................................................................................ 28 3.2.4 Interdigitated substrates ................................................................................................. 28 3.3 Instrumental Information of the Used Techniques ............................................................... 28 3.3.1 X-ray diffraction ............................................................................................................ 28 3.3.2 Infrared reflection absorption spectroscopy................................................................... 29 3.3.3 Raman spectroscopy ...................................................................................................... 29 3.3.4 UV-vis spectroscopy ...................................................................................................... 29 3.3.5 ToF-SIMS ...................................................................................................................... 29 3.3.6 MALDI-ToF/MS ........................................................................................................... 30 3.3.7 SEM and EDX ............................................................................................................... 31 3.3.8 AFM ............................................................................................................................... 31 3.3.9 Electrical conductivity measurements ........................................................................... 31 3.3.10 Quartz crystal microbalance ........................................................................................ 32 4. RESULTS ................................................................................................................................. 33 4.1 Tth and EDOT Polymerization in SURMOF-2 Structures ................................................... 33 4.1.1 Background .................................................................................................................... 33 4.1.2 SURMOF-2 preparation ................................................................................................ 34 4.1.3 Monomer loading and polymerization ins SURMOF-2 ................................................ 35 4.1.4 Results and discussion ................................................................................................... 35 4.1.4.1 Oligomerization of Tth in SURMOF-2 .................................................................. 36 4.1.4.2 Oligomerization of EDOT in SURMOF-2 ............................................................. 41 4.1.5 Summary ................................................................................................................... 46 4.2 Methyl Propiolate Polymerization in Different Type of SURMOFs ................................... 47 4.2.1 Background .................................................................................................................... 47 4.2.2 SURMOF preparation .................................................................................................... 47 4.2.3 Monomer loading and polymerization in SURMOF ..................................................... 48 4.2.4 Modelling the SURMOF structures by loading MP and Pd .......................................... 48 4.2.5 Simulation of methyl propiolate .................................................................................... 49 4.2.6 Results and discussion ................................................................................................... 49 4.2.7 Summary ........................................................................................................................ 62 5. CONCLUSION AND OUTLOOK ......................................................................................... 63 6. APPENDIX ............................................................................................................................... 67 6.1 Appendix A .......................................................................................................................... 67 6.2 Appendix B ........................................................................................................................... 70 6.3 Appendix C ........................................................................................................................... 79 7. REFERENCES......................................................................................................................... 83 PUBLICATIONS ......................................................................................................................... 97 CURRICULUM VITAE .............................................................................................................. 98 ACKNOWLEDGEMENTS ......................................................................................................... 99 ABSTRACT The work performed within this thesis aims towards templated polymerization reactions in the confined pore space of surface-mounted metal-organic frameworks