Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München Syntheses of Multinary Lithium (Oxo)nitridosilicates Saskia Lupart aus Augsburg, Deutschland 2012 Erklärung Diese Dissertation wurde im Sinne von § 7 der Promotionsordnung vom 28. November 2011 von Herrn Prof. Dr. W. Schnick betreut. Eidesstattliche Versicherung Diese Dissertation wurde eigenständig und ohne unerlaubte Hilfe erarbeitet. München, 30.03.2012 ............................................................................. (Saskia Lupart) Dissertation eingereicht am 30.03.2012 1. Gutacher Prof. Dr. W. Schnick 2. Gutachter Prof. Dr. O. Oeckler Mündliche Prüfung am 26.04.2012 Meiner Familie Acknowledgement First of all, I would like to express my gratitude to Prof. Wolfgang Schnick for offering me this extremely interesting research project in his group. Especially I would like to thank him for the nice working atmosphere, the freedom in research, the trust he puts into his coworkers, his always open ear, the helpful and sometimes very funny discussions (because he obviously can make sense) and the continuing encouragement and support during this work. For being my second referee, I thank Prof. O. Oeckler. Furthermore, I would like to thank him for support in almost all situations during my PhD as well as inspiring discussions and help with crystallographic questions. I am thankful to Prof. H.-C. Böttcher, Prof. D. Johrendt, Prof. K. Karaghiosoff and Prof. W. Schmahl for being available as examiners in my viva-voce. For analytical measurements and help with the hardware I would like to thank the following persons (in alphabetical order): Dr. P. Mayer, T. Miller, C. Minke, Prof. O. Oeckler, W. Wünschheim, and Dr. J. Schmedt auf der Günne. For the conduction of lithium ion conductivity measurements and helpful discussions about this subject I would like to thank Prof. Dr. J. Maier and especially Dr. G. Gregori (both MPI Stuttgart) who is the best cooperation partner. I am indebted to my research students: S. Johansson, K. Fenzke, D. Durach, E. Flügel and A. Zimpel. I want to thank especially D. Durach and wish her all the best for her master thesis and the following PhD thesis. Special thanks to my lab-mates and the nice working atmosphere in lab D2.100. Especially to T. Schröder with whom I had the honor to share a bench although after all this time I am still not able to distinguish between all the metal-music styles; for me he is the best melodic death metal guy in the world. Furthermore, I would like to thank M. Seibald and F. Hintze for all the fun we had. I would like to thank all my colleagues of the solid-state group for the nice working atmosphere and countless helpful discussions. In detail I would like to thank Dr. S. Pagano who started the research field of lithium nitridosilicates (and the countless smoothies to activate my grey cells) and left some things to do for me. Great thanks go to Dr. M. Tegel who helped me a lot starting in the solid-state group. To Dr. S. Sedlmaier I am indebted for interesting discussions about almost everything, preferable accompanied by a good dinner with good wine. Dr. C. Höller I want to thank for all his encouraging “telephone-jokes”. Furthermore, I would like to thank Dr. A. Zurawski, with whom I had helpful discussions, but also a lot of fun. T. Rosenthal I thank for his always open ear. Thanks also go to F. Pucher who shares my hobby and joined me early Sunday mornings at the fish-market. D. Baumann I thank for being my Glovebox-Buddy and the interesting discussions about the wonderful world of nitrogen. N. Braml, S. Schmiechen and P. Pust I would like to thank for the lunch pauses. S. Schmiechen I would like to thank further for trying out my ideas, although he had great doubts at first. I would like to thank Matthias in whom I found true love and who supported and encouraged me during my thesis. Above all I would like to thank my mother without her love, understanding and help in every situation I wouldn’t be here. Great thanks go to my sister, the best sister on the world. I am among those who think that science has great beauty. A scientist in his laboratory is not only a technician: he is also a child placed before natural phenomena which impress him like a fairy tale. (Marie Curie) Table of Contents 1 Introduction .................................................................................................. 1 2 Lithium Alkaline-Earth Nitridosilicates .................................................... 8 2.1 Overview ........................................................................................................................... 8 2.2 Tuning the Dimensionality of Nitridosilicates in Lithium Melts ............................... 13 2.2.1 Introduction ............................................................................................................................................. 14 2.2.2 Results and Discussion ............................................................................................................................ 14 2.2.3 Conclusion ............................................................................................................................................... 20 2.2.4 Experimental Section .............................................................................................................................. 20 2.2.4.1 X-ray diffraction .............................................................................................................................. 20 2.2.4.2 Solid-state MAS NMR ...................................................................................................................... 21 2.2.4.3 Microanalysis .................................................................................................................................. 21 2.2.4.4 Synthesis .......................................................................................................................................... 21 2.2.5 References ............................................................................................................................................... 22 2.3 Li4Ca3Si2N6 and Li4Sr3Si2N6 – Quaternary Lithium Nitridosilicates with Isolated 10- [Si2N6] Ions .......................................................................................................................... 26 2.3.1 Introduction ............................................................................................................................................. 27 2.3.2 Results and Discussion ............................................................................................................................ 27 2.3.3 Conclusions ............................................................................................................................................. 31 2.3.4 Experimental Section .............................................................................................................................. 31 2.3.4.1 Synthesis .......................................................................................................................................... 31 2.3.4.2 X-ray Diffraction ............................................................................................................................. 32 2.3.4.3 Microanalysis .................................................................................................................................. 32 2.3.5 References ............................................................................................................................................... 33 7- 2.4 LiCa3Si2N5 – A Lithium Nitridosilicate with a [Si2N5] double-chain ...................... 34 2.4.1 Introduction ............................................................................................................................................. 35 2.4.2 Results and Discussion ............................................................................................................................ 35 2.4.2.1 Crystal Structure Description .......................................................................................................... 35 2.4.2.2 Lattice Energy Calculations According to the MAPLE Concept ..................................................... 39 2.4.2.3 Solid-state MAS NMR ...................................................................................................................... 40 2.4.3 Conclusions ............................................................................................................................................. 42 2.4.4 Experimental Section .............................................................................................................................. 42 2.4.4.1 Synthesis .......................................................................................................................................... 42 2.4.4.2 Chemical Analyses ........................................................................................................................... 43 2.4.4.3 Single Crystal X-ray Analysis .......................................................................................................... 43 2.4.4.4 X-ray Powder Diffraction ................................................................................................................ 43 2.4.4.5 Solid-state MAS NMR .....................................................................................................................