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Clusters and Networks of Tetrel Elements and Late D Block Metals in Ternary Intermetallic Phases with Alkali and Alkaline Earth Metals

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Clusters and Networks of Tetrel Elements and Late D Block Metals in Ternary Intermetallic Phases with Alkali and Alkaline Earth Metals Clusters and Networks of Tetrel Elements and Late d Block Metals in Ternary Intermetallic Phases with Alkali and Alkaline Earth Metals Saskia Stegmaier Technische Universität München Lehrstuhl für Anorganische Chemie mit Schwerpunkt Neue Materialien TECHNISCHE UNIVERSITÄT MÜNCHEN Lehrstuhl für Anorganische Chemie mit Schwerpunkt Neue Materialien Clusters and Networks of Tetrel Elements and Late d Block Metals in Ternary Intermetallic Phases with Alkali and Alkaline Earth Metals Saskia Stegmaier Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigten Dissertation. Vorsitzender: Univ.-Prof. Dr. Lukas Hintermann Prüfer der Dissertation: 1. Univ.-Prof. Dr. Thomas F. Fässler 2. Univ.-Prof. Dr. Karsten Reuter 3. Univ.-Prof. Dr. Hubert Schmidbaur (em.) Die Dissertation wurde am 12.04.2012 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 25.05.2012 angenommen. … – and yet – and yet – it’s rather curious, you know, this sort of life! Alice (in Wonderland) / Lewis Carroll Dank sage ich meinem Doktorvater Prof. Dr. Thomas F. Fässler für Vertrauen, Wohlwollen, Unterstützung und wissenschaftliche Freiheit. Dr. Lisa Siggelkow für die Labor-, Büro- und Diskussionsgemeinschaft, für die sorgfältige Durchsicht und wertvolle Vorschläge zu Manuskripten dieser Arbeit sowie für Unterhaltung(en) in und außerhalb der Festkörperchemie. Dr. Bernhard Wahl für Interesse und Unterstützung nicht nur in speziellen kristallographischen Lagen. Markus Waibel für die Bürogemeinschaft, den Aufbau der neuen IT-Netzwerkstruktur am Lehrstuhl und insbesondere für das Auflösen meiner Cluster-Phasen. Dr. M. Bele Boeddinghaus für die SQUID-Betreuung und für gemeinsame Unternehmungen und die gute Zeit in München und anderswo. Dr. Viktor Hlukhyy für viele Gespräche und Anregungen zu festkörperchemischen Belangen. Dr. Wilhelm Klein insbesondere für die Diskussionsbereitschaft zu kristallo- graphischen Fragen. Dr. Sung-Jin Kim für die Einführung in festkörperchemische Arbeits- weisen. Manuela Donaubauer für die Hilfe bei den organisatorischen Aspekten. den Gruppen Fässler , Kraus , Niewa und Nilges . meinem Bachelor- und später Master-Studenten Alexander Henze und meinen Forschungs- praktikanten Richard Brimioulle , Jürgen Kraus und Thomas Wagner , sowie unserem Auszubildenden und später Laboranten Fabian Krause für ihr Engagement und die zu den jeweiligen Projekten geleisteten Beiträge. der Studienstiftung des Deutschen Volkes für die Gewährung eines Promotionsstipendiums. der Technischen Universität München für ein Promotionsstipendium im Rahmen des Hochschul- und Wissenschaftsprogramms (HWP). Acknowledgments Dank sage ich Dr. Andreas Kaltzoglou unter anderem für die Einarbeitung an der DTA, Priv.-Doz. Dr. Florian Kraus für viele wertvolle Hinweise und Rubidium, Dr. Sandra Scharfe und Volodymyr Baran für geseigertes Natrium und Kalium, Prof. Dr. Tom Nilges für die stete Diskussionsbereitschaft, Dr. Antti J. Karttunen für Gespräche und Interesse nicht nur die theoretischen Teile dieser Arbeit betreffend, Andrea Hoffmann und Ingrid Werner für REM-Bilder, EDX- und SQUID-Messungen, Laura-Alice Jantke für die Zusammenarbeit an der gemeinsamen Publikation, Dr.-Ing. Stephan D. Hoffmann für die Einarbeitung am Oxford Diffraktometer. Sebastian Baer, Christian Benda, Dr. Daniel Bräunling, Carina Dressel, Dr. Michael Evans, Dr. Frank Gäbler, Haiyan He, Thomas Henneberger, Dr. Florian Kiefer, Iryna Kurylyshyn, Dr. Prashanth W. Menezes, Dieter Rau, Dr. Annette Schier, Ursula Madan-Singh, Herta Slavik, Dr. Annette Spiekermann, Lorenzo Toffoletti, Dr. Jian-Qiang Wang, Patrick Woidy, Michael Zeilinger und allen anderen Mitgliedern der Gruppen Fässler , Kraus , Niewa und Nilges für die Zusammenarbeit, ihre Hilfsbereitschaft und gemeinsame Unternehmungen. auch allen anderen, insbesondere Mitarbeitern der Fakultät für Chemie der Technischen Universität München, die zum Gelingen dieser Arbeit beigetragen haben. meinen Freunden und meiner Familie . Zusammenfassung (Halb)metalle des p-Blocks ( E) können zusammen mit späten d-Block-Metallen ( T) und elektropositiven Metallen ( A’) intermetallische Phasen bilden, die als aus A’ -Kationen und einer insgesamt negativ geladenen T–E-Teilstruktur bestehend beschrieben werden können. Diese A’ –T–E-Phasen beeindrucken durch eine große Vielfalt an Strukturen und Bindungs- verhältnissen. Gegenstand der vorliegenden Arbeit sind A’ –T–Tt -Phasen ( E = Tt ; Tt : Tetrel- element), die Cluster, Clustersäulen oder Netzwerke als T–Tt -Teilstrukturen aufweisen. Na 2.8 Cu 5Sn5.6 und A12 Cu 12 Sn 21 (A = Na, K, Rb, Cs), die ersten A–Cu–Sn-Phasen mit A = Na – Cs, weisen intermetalloide Cu–Sn-Clusterspezies auf, die in der Clusterchemie der (Halb)metalle der Gruppe 14 bislang einzigartig sind. In der Struktur von Na 2.8 Cu 5Sn 5.6 liegen 1 diskrete doppelwandige Cu–Sn-Säulen ∞{Sn 0.6 @Cu 5@Sn 5} vor, die zu quasi-ein- dimensionalen metallischen Eigenschaften führen. Die isotypen A12 Cu 12 Sn 21 -Phasen enthalten 12− mehrschalige Cluster [Sn@Cu 12 @Sn 20 ] mit delokalisierter Clusterbindung. Die A–Cu–Sn- Verbindungen wurden durch Reaktion von Alkalimetallen mit zuvor hergestellten Cu–Sn- Legierungen synthetisiert und können – in Analogie zu Zintl-Verbindungen – als „salzartig“, mit Alkalimetall-Kationen und intermetalloiden Cu–Sn-Polyanionen, angesehen werden. {T@Tt n}-Cluster mit einem endoedrischen T-Atom in einem {Tt n}-Käfig sind aus der Chemie der Zintlanionen in Lösung bekannt. Im Rahmen dieser Arbeit wurden Berechnungen zur 3− 3− 3− Analyse der (elektronischen) Struktur von [Cu@Sn 9] , [Ir@Sn 12 ] und [Co@Ge 10 ] durchgeführt. Für einen Übersichtsartikel wurde ein Beitrag über theoretische Untersuchungen zu bestimmten Clusterspezies der Tetrelelemente verfasst. Die ternäre Phase 4− 4− Na 12 NiSn 17 mit den Clusteranionen [Ni@Sn 9] und [Sn 4] ist eine der ersten strukturell charakterisierten Festkörperphasen mit { T@Tt n}-Clustern. 4− Die Verbindungen A14 ZnGe 16 (A = K, Rb) weisen [Ge 4] -Anionen und ein neues Isomer des 6− Clusters [(Ge 4)Zn(Ge 4)] auf, welcher aus zwei tetraedrischen { Tt 4}-Einheiten und einem diese verknüpfenden T-Atom besteht. {( Tt 4)T(Tt 4)}-Strukturmotive sind von einer Reihe von Festkörperphasen bekannt. Besonderes Interesse verdienen die ternären A14 ZnGe 16 - Verbindungen da sie zu den wenigen löslichen Zintl-Phasen mit { Tt 4}-Einheiten zählen. Zusammenfassung Die A–Zn–Tt -Phasen ( A = Li, Na; Tt = Ge, Sn) Li 2ZnGe 3, Li 3Zn 2Sn 4, Na 8Zn 4Ge 42 und Na 2ZnSn 5 weisen verschiedene Zn–Tt -Netzwerke vierbindiger Atome auf. Li 2ZnGe 3 und Li 3Zn 2Sn 4 bestehen aus Zn–Tt -Netzwerken mit diamant(polytyp)artigen Strukturen deren Zwischenräume mit Li-Atomen aufgefüllt sind. Na 8Zn 4Ge 42 besitzt eine Typ-I Clathrat- Struktur mit Na-Atomen in den käfigartigen Hohlräumen des Zn–Ge-Netzwerkes. Im Fall von hP - und tI -Na 2ZnSn 5 liegen offene Zn–Sn-Netzwerkstrukturen vor, die Kanäle aufweisen, welche mit Na-Atomen besetzt sind. Der Polymorphismus der Zintl-Verbindung Na 2ZnSn5 wurde im Rahmen dieser Arbeit aufgezeigt und untersucht. Der Phasenübergang von der metastabilen Modifikation hP -Na 2ZnSn 5 zur stabilen Modifikation tI -Na 2ZnSn 5 konnte mittels Röntgenbeugungs- experimenten am Pulver und am Einkristall in situ beobachtet werden. Des Weiteren wurde die Beziehung zwischen Na 2ZnSn 5 und Na 5Zn 2+ xSn 10−x untersucht. Ausgehend von einer Analyse der Zn–Sn-Netzwerkstrukturen dieser Phasen wurde ein Konstruktionsprinzip für eine Serie von Netzwerken vierbindiger Atome entwickelt. Diese Netzwerke können, beispielsweise in theoretischen Studien, als Strukturen hypothetischer Allotrope der Tetrelemente C, Si, Ge und Sn betrachtet werden. In den ternären Ae –Zn–Sn-Systemen mit den Erdalkalimetallen Ae = Ca und Sr wurden Ca 2Zn 3Sn 6 und SrZn 2Sn 2 erhalten. Diese Verbindungen sind typische polare intermetallische Phasen mit Zn–Sn-Netzwerken, die auch Atome mit Koordinationszahlen größer vier enthalten. Die Synthese der intermetallischen Phasen erfolgte ausgehend von den Elementen über Hochtemperatur-Reaktionen. Kristallstrukturbestimmungen wurden mittels Röntgen- beugungsexperimenten an Einkristallen durchgeführt. Zu den verwendeten experimentellen Charakterisierungsmethoden zählen des Weiteren Röntgenpulverdiffraktometrie, energie- dispersive Röntgenspektroskopie (EDX) zur qualitativen und semi-quantitativen chemischen Analyse, thermische Analyse (DTA) und SQUID-Magnetometrie. Berechnungen der elektronischen Struktur von Festkörperverbindungen wurden mit dem Stuttgarter TB-LMTO- ASA Program durchgeführt. Für Berechnungen der (elektronischen) Struktur diskreter polyanionischer Cluster wurden GAUSSIAN und DGRID verwendet, letzteres für Berechnungen der Elektronenlokalisierungsfunktion (ELF). Abstract Intermetallic phases of p block (semi)metals ( E), late d block metals ( T), and electropositive metals ( A’ ) which can be described in terms of A’ cations and an overall negatively charged T–E substructure show an impressive variety of structures and bonding situations. The present thesis deals with A’ –T–Tt ternary phases ( E = Tt ; Tt : tetrel element) that feature T–Tt clusters, rods or networks. Intermetalloid Cu–Sn cluster species that are unprecedented in the cluster chemistry of the group 14 (semi)metals are exhibited by Na 2.8 Cu 5Sn 5.6 and A12 Cu 12 Sn 21 (A = Na, K, Rb, Cs), which represent the first A–Cu–Sn phases with A = Na to Cs. Na 2.8 Cu 5Sn 5.6 shows discrete
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