Substitution effects in binary intermetallic compounds [Elektronische Ressource] : investigations in the systems alkali and alkaline earth metal - tin and alkaline earth metal - bismuth / Sung-Jin Kim

Informations

• Publié par: technische_universitat_munchen
• Publié le: 01 janvier 2007
• Nombre de lectures: 42
• Langue: English
• Poids de l'ouvrage: 18 Mo

Extrait

Substitution Effects in Binary Intermetallic Compounds:
Investigations in the System Alkali and Alkaline-Earth Metal – Tin
and
Alkaline-Earth Metal – Bismuth


Sung-Jin Kim



Technische Universität München
Lehrstuhl für Anorganische Chemie
mit Schwerpunkt Neue Materialien

November 2007 Technische Universität München
Lehrstuhl für Anorganische Chemie mit Schwerpunkt Neue Materialien

Substitution Effects in Binary Intermetallic Compounds:
Investigations in the System Alkali and Alkaline-Earth Metal – Tin
and
Alkaline-Earth Metal – Bismuth

Sung-Jin Kim

Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität
München zur Erlangung des akademischen Grades eines

Doktors der Naturwissenschaften
genehmigten Dissertation.
Vorsitzende: Univ.-Prof. Dr. Sevil Weinkauf
Prüfer der Dissertation:
1. Univ.-Prof. Dr. Thomas Fässler
2. Univ.-Prof. Dr. Ulrich K. Heiz
3. Univ.-Prof. Dr. Klaus Köhler

Die Dissertation wurde am 05.11.2007 bei der Technischen Universität München
eingereicht und durch die Fakultät für Chemie am 06.12.2007 angenommen.

Acknowledgments

 To my supervisor Prof. Dr. Thomas F. Fässler for accepting me as a PhD
student, the interesting topic, valuable advices, patience, and guidance in
difficult situations.
 Dr.-Ing. Stephan D. Hoffmann, for introducing me to single-crystal X-ray
diffraction techniques as well as for the valuable discussions, SQUID
measurements, and advices in every respect.
 I am particularly indebted to Dr. Siméon Ponou, for introducing me to the
‘Endless Wonders’ of Zintl chemistry and fruitful discussions.
 Dr. Martin Schreyer, for introducing me to powder X-ray diffraction methods.
 Dr. Florian Kraus, for the Gaussian calculations and general advices.
 Prof. Dr. R. Niewa, for the discussions of DTA experiments.
 Ingrid Werner, for helping out with the EDX measurements.
 Dr. Matthias Opel (Walther-Meissner-Institut, TU-München) and Dipl.-Chem.
Bele Boeddinghaus for the SQUID measurements.
 Special thanks go to M. Sc. Andreas Kaltzoglou, Dipl.-Chem. Annette
Spiekermann, and Dipl.-Chem. Saskia Stegmaier for reading and correcting
the manuscript.
 Dipl.-Chem. Annette Spiekermann, for solution experiments with my
compounds.
 M. Sc. Andreas Kaltzoglou, for the time in the ‚Praktikum für
Lebensmittelchemiker’ and many discussions.
 To all other co-workers during my time in Prof. Fässler’s group: Sebastian
Baer (my ‘Knecht’), Dr. Frank Dubois, M. Sc. Magreth A. Fredricks, Dr. Viktor
Hlukhyy (for his experimental advices), M. Sc. Florian Kiefer, Ursula Madan-
Singh, Dipl.-Chem. Sandra Scharfe, Dipl.-Chem. Lisa Siggelkow, Dr. Jian-
Qiang Wang, and Dr. Li Yong.
 Finally, my parents deserve my deepest gratitude for their eternal
understanding, support, and lenience.

i

Table of Contents
1 General Introduction 1
1.1 Classes of Intermetallic Compounds 2
1.1.1 Zintl Phases 3
1.1.2 Polar Intermetallics 7
1.2 The Element Sn in Intermetallic Compounds 8
1.3 References 9
2 Scope and Outline of this Work 12
3 Experimental and Analytical Methods 14
3.1 Synthesis 14
3.2 X-ray Diffraction Experiments 16
3.2.1 Powder X-ray Diffraction 16
3.2.2 Single-Crystal X-ray Diffraction 17
3.3 SEM and EDX 19
3.4 DTA 20
3.5 Magnetic Measurements (SQUID) 21
3.6 Computational Methods 21
3.7 References 24
4 Substitution Effects in the Binary System Na–Sn with Zn 26
4.1 Introduction 26
4.2 Na ZnSn and NaZn Sn - Open Framework Phases with 2 5 0.3 2.7(1)
Zeolite-like Structures 29
4.2.1 Synthesis and Characterization 29
4.2.2 Crystal Structure Determination and Description of Na ZnSn 2 5
and NaZn Sn 33 0.3 2.7(1)
4.2.3 Electronic Structure of Na ZnSn 39 2 5
4.2.4 Discussion 42
4.3 Na Zn Sn (x = 0.28) - An Intermediate Phase between the α-Sn 5 2+x 10–x
and Half-Heusler Structure 47
4.3.1 Synthesis and Characterization 47
4.3.2 Crystal Structure Determination and Description 48
4.3.3 Electronic Structure 54
4.3.4 Discussion 56
4.4 Na Zn Sn - A Zintl Phase with a New Type of Sn Polyhedron 60 29 24 32
4.4.1 Synthesis and Characterization 60
4.4.2 Crystal Structure Determination and Description 62
4.4.3 Electronic Structure 68
4.4.4 Discussion 69ii Table of Contents

4.5 Synthesis and Crystal Structure of Na Zn Sn - Icosahedral 16 13.54 13.47(5)
Linking through Triangular Motifs 74
4.5.1 Synthesis and Characterization 74
4.5.2 Crystal Structure Determination and Description 75
4.5.3 Discussion 81
4.6 Synthesis and Crystal Structures of Na Zn Sn and 22 20 19(1)
Na Zn Sn - Two Cluster Compounds with Structures 34 65 40(1)
Analogous to Gallides without an Element of Group 13 83
4.6.1 Synthesis of Na Zn Sn and Na Zn Sn 8422 20 19(1) 34 65 40(1)
4.6.2 Crystal Structure Determination of
Na Zn Sn and Na Zn Sn 84 22 20 19(1) 34 65 40(1)
4.6.3 Crystal Structure Description and Discussion of Na Zn Sn 87 22 20 19(1)
4.6.4 Crystal Structure ion andsion of Na Zn Sn 93 34 65 40(1)
4.7 Na ZnSn and Na K ZnSn (x = 1.77) - {ZnSn } Units with 16 Valence 6 2 6–x x 2 2
Electrons 102
4.7.1 Synthesis and Characterization 102
4.7.2 Crystal Structure Determination and Description of Na ZnSn and 6 2
Na K ZnSn 1064.23 1.77(1) 2
4.7.3 Electronic Structure of Na ZnSn 1126 2
4.7.4 Discussion and Results of Molecular Calculations 115
4.8 Synthesis and Crystal Structure of Na Zn Sn - An Intergrowth 20 8 11
Structure Made of Electron Deficient and Electron Precise Layers 120
4.8.1 Synthesis and Characterization 120
4.8.2 Crystal Structure Determination and Description 121
4.8.3 Discussion 126
4.9 General Discussion 129
4.10 References 133
5 Substitution Effects in Sr Bi and Sr Sn 136 2 3 3 5
5.1 The System Sr Ba Bi (0 ≤ x ≤ 1.3) - Structural Distortions 2–x x 3
Induced by Chemical Pressure 136
5.1.1 Introduction 136
5.1.2 Synthesis and Characterization 137
5.1.3 Crystal Structure Determination and Description of Sr Bi and 2 3
Sr Ba Bi 140 2 –x x 3
5.1.4 Electronic Structure 148
5.1.5 Magnetic Properties 153
5.1.6 Discussion 154
5.2 Substitution Effects in Sr Sn : Synthesis, Structure, and Electronic 3 5
Effects in Sr Sn Bi 158 3 3.36 1.64(3)
5.2.1 Introduction 158
5.2.2 Synthesis and Characterization 159
5.2.3 Crystal Structure Determination and Description 160 Table of Contents iii

5.2.4 Electronic Structure 164
5.2.5 Discussion 168
5.3 Substitution Effects in Sr Sn : Synthesis and Structure of 3 5
Sr Sn Tl (x = 1.78, 2.14) and Sr Sn In (x = 1.18) 170 3 5–x x 3 5–x x
5.3.1 Introduction 170
5.3.2 Synthesis and Characterization 171
5.3.3 Crystal Structure Determination and Description 172
5.3.4 Discussion 178
5.4 Substitution Effects in Sr Sn : Na SrSn - A Polar Intermetallic 3 5 2 4
Compound with a Novel Sn Substructure 180
5.4.1 Introduction 180
5.4.2 Synthesis and Characterization 181
5.4.3 Crystal Structure Determination and Description 182
5.4.4 Electronic Structure 187
5.4.5 Discussion 190
5.5 References 192
6 Synthesis and Characterization of the Binary Phases K Sn , 70 103
BaSn , and Ae Tl (Ae = Ca, Sr) 194 2 3 5
4– 2– 6.1 K Sn - A Zintl Phase Containing Isolated {Sn } , {Sn } , 70 103 9 5
4– and {Sn } Wade Clusters 194 4
6.1.1 Introduction 194
6.1.2 Synthesis and Characterization 195
6.1.3 Crystal Structure Determination and Description 197
6.2 BaSn - A Zintl Phase with α-Arsenic like Sn Layers 205 2
6.2.1 Introduction 205
6.2.2 Synthesis and Characterization 205
6.2.3 Crystal Structure Determination and Description 208
6.2.4 Electronic Structure 210
6.2.5 Discussion 212
6.3 Ae Tl (Ae = Ca, Sr) - Two Intermetallic Phases 3 5
with Pu Pd Structure 213 3 5
6.3.1 Introduction 213
6.3.2 Synthesis and Characterization 214
6.3.3 Crystal Structure Determination and Description 216
6.3.4 Electronic Structure 221