Oxoselenates(IV) of the trivalent rare-earth elements and some derivatives [Elektronische Ressource] / vorgelegt von Joseph Wontcheu

Informations

• Publié par: universitat_stuttgart
• Publié le: 01 janvier 2004
• Nombre de lectures: 11
• Langue: English
• Poids de l'ouvrage: 26 Mo

Extrait

Oxoselenates(IV) of the Trivalent Rare-Earth
Elements and Some Derivatives



Von der Fakultät Chemie der Universität Stuttgart
zur Erlangung der Würde eines Doktors der
Naturwissenschaften (Dr. rer. nat.) genehmigte Abhandlung


vorgelegt von
Joseph Wontcheu
aus Bafang (Kamerun)



Hauptberichter: Prof. Dr. Thomas Schleid
Mitberichter: Dr. Paul Keller
weiterer Prüfer: Dr. Klaus Müller
Prüfungsvorsitzender: Prof. Dr. Gerd Becker


Tag der mündlichen Prüfung: 23. April 2004


Institut für Anorganische Chemie der Universität Stuttgart

2004 Pledge 1
Pledge

I certify that the present dissertation entitled:
"Oxoselenates(IV) of the Trivalent Rare-Earth Elements and Some Derivatives" was carried
out without any unlawful devices. I did not use any other than the described literature sources
or technical devices. This work has never been submitted before in this or similar form to any
other university and has not been used for any examination.


Joseph Wontcheu




















2 Acknowledgements
Acknowledgements

I would like to express my profound gratitude to Prof. Dr. Thomas Schleid for giving me
opportunity to do this work in his laboratory and who, despite his charged work programme,
accepted to supervise this dissertation.
I am also greatly indebted to:
Prof. Dr. Paul Keller
Prof. Dr. Klaus Müller
Prof. Dr. Gerd Becker, for the examination.
I would also like to thank: Christof Schneck for always giving me very new literature data
during the course of this work, Dipl. Chem. Sabine Strobel, Dr. Hagen Grossholz, Dr. Steffen
F. Meier for their continuous encouragements, friendliness, care and company and whose
comments were very helpful.

I also thank Sumati Panicker-Otto for correcting the English language.

My gratitudes also go to Dr. Falk Lissner, Dr. Helge Müller Bunz, Dr. Ingo Hartenbach for
the single crystal measurement.

I also wish to thank Prof. Dr. Emmanuel Ngameni, Dr. Ketcha Joseph Mbadcam, Dr. Paul
Mingo Ghogomu (University of Yaounde I), for their advice and support in my application
for the scholarship.

I appreciate and thank all Doctorates students of our research group, whose long experience in
the laboratory was of great relief for me.

My heart-felt thanks go to my friend Mambe Fotsing Clarisse, whose moral support,
generosity, advice, encouragement and permanent contact contributed emensely to the
realisation of this work.

Finally I’m grateful to Flaubert Mbeunkui who kept me company and with whom I shared
more time in Stuttgart.
Table of contents 3
Table of contents

1 Introduction 7
2 Generalities on the working methods 10
2.1 Use of apparatuses 10
2.1.1 Argon glove-box
2.1.2 Inert gas and vacuum equipment 11
2.2 Structure investigations by means of X-ray diffraction 12
2.2.1 Powder diffractometer 12
2.2.2 Single crystal investigations 13
2.2.2.1 Rotation and oscillation photographs 13
2.2.2.2 The Weissenberg camera 14
2.2.2.3 The IPDS (Image Plate Diffraction System) single crystal diffractometer 15
2.2.2.4 The CCD (Charge Coupled Device) single crys 16
2.2.3 Structure solution and refinement 17
2.3 Synthesis methods 19
2.3.1 Chemicals used
2.3.2 Reaction guidance 20
2.3.3 Devices and computer programs 21
3 Oxoselenates(IV) of the trivalent rare-earth elements 23
3.1 Prefaces and synthesis methods 23
3.2 Structure description of the hexagonal Sc [SeO ] 25 2 33
3.2.1 Structural data for the hexagonal Sc [SeO ] 30 2 33
3.3 Structure description of the orthorhombic Ce [SeO ] 33 2 3 3
3.3.1 Structural data for the orthorhombic Ce [SeO ] 36 2 33
3.4 Structure description of the monoclinic Pr [SeO ] 39 2 33
3.4.1 Structural data for the monoclinic Pr [SeO ] 43 2 33
3.5 Structure description of the triclinic M [SeO ] (M = Y, Sm – Ho, Tm – Lu) 50 2 3 3
3.5.1 Structural data for the triclinic M [SeO ] (M = Y; Sm – Ho, Tm – Lu) 56 2 3 3
4 Oxide oxoselenates(IV) of the trivalent rare-earth elements 73
4.1 Prefaces and synthesis methods 73
4.2 Structure description of M O[SeO ] (M = Sm – Tm) 742 3 24 Table of contents
4.3 Structural data for M O[SeO ] (M = Sm – Tm) 80 2 3 2
5 Oxyhalide oxoselenates(IV) of the trivalent rare-earth elements 87
5.1 Compounds of the formula M O Cl[SeO ] (M = Tb, Dy, Er) 88 3 2 3 2
5.1.1 Synthesis of M O Cl[SeO ] (M = Tb, Dy, Er) 88 3 2 3 2
5.1.2 Structure description of the orthorhombic M O Cl[SeO ] (M = Tb, Dy) 89 3 2 3 2
5.1.3 Structure description of the monoclinic M O Cl[SeO ] (M = Er) 90 3 2 3 2
5.1.4 Structural analogies 91
5.1.5 Structural data for M O Cl[SeO ] (M = Tb, Dy, Er) 97 3 2 3 2
5.2 Compounds of the formula M O Cl [SeO ] 102 4 3 2 3 2
5.2.1 Synthesis of M O Cl [SeO ] (M = Er, Yb) 4 3 2 3 2
5.2.2 Structure description of M O Cl [SeO ] (M = Er, Yb) 103 4 3 2 3 2
5.2.3 Structural data for M O Cl [SeO ] 109 4 3 2 3 2
5.3 Structure of Gd O Br [SeO ] and Tb O Cl [SeO ] 120 5 4 3 3 2 5 4 3 3 2
5.3.1 Synthesis of Gd O Br [SeO ] and Tb O Cl [SeO ] 5 4 3 3 2 5 4 3 3 2
5.3.2 Structure description of Gd O Br [SeO ] and Tb O Cl [SeO ] 120 5 4 3 3 2 5 4 3 3 2
5.3.3 Structural data for Gd O Br [SeO ] and Tb O Cl [SeO ] 125 5 4 3 3 2 5 4 3 3 2
5.4 Structure of M O Br [SeO ] (M = La, Pr) and M O Cl [SeO ] (M = Pr, 9 8 3 3 4 9 8 3 3 4
Nd, Sm, Gd) 130
5.4.1 Synthesis methods
5.4.2 Structure description 131
5.4.3 Structural data 137
6 An alkali metal oxoselenate(IV) of a trivalent rare-earth element:
Li Lu [SeO ] 152 3 5 3 9
6.1 Synthesis of Li Lu [SeO ] 3 5 3 9
6.2 Structure description of Li Lu [SeO ] 152 3 5 3 9
6.3 Structural data for Li Lu [SeO ] 157 3 5 3 9
7 An alkali metal halide oxoselenate(IV) of a trivalent rare-earth element:
CsTmCl [SeO ] 166 2 3
7.1 Synthesis of CsTmCl [SeO ] 2 3
7.2 Structure description of CsTmCl [SeO ] 166 2 3
7.3 Structural data for CsTmCl [SeO ] 171 2 3
8 An alkali metal oxyhalide oxoselenate(IV) of a trivalent rare-earth element: Table of contents 5
CsEu O Cl [SeO ] 174 4 3 3 32
8.1 Synthesis of CsEu O Cl [SeO ] 174 4 3 3 3 2
8.2 Structure description of CsEu O Cl [SeO ] 174 4 3 3 3 2
8.3 Structural data for CsEu O Cl [SeO ] 180 4 3 3 3 2
9 Summary and outlook 185
9.1 Results 185
9.1.1 Oxoselenates(IV) of the trivalent rare-earth elements 186
9.1.1.1 The hexagonal Sc [SeO ] 186 2 3 3
9.1.1.2 The orthorhombic Ce [SeO ] 186 2 3 3
9.1.1.3 The monoclinic Pr [SeO ] 187 2 3 3
9.1.1.4 The triclinic M [SeO ] (M = Y; Sm – Lu) 187 2 3 3
9.1.2 Oxide oxoselenates(IV) of the trivalent rare-earth elements 188
9.1.3 Oxide halide oxoselenates(I 189
9.1.3.1 Compounds of the formula M O Cl[SeO ] (M = Tb, Dy, Er) 190 3 2 3 2
9.1.3.2 O Cl [SeO ] (M = Er, Yb) 190 4 3 2 3 2
9.1.3.3 Structure of Gd O Br [SeO ] and Tb O Cl [SeO ] 191 5 4 3 3 2 5 4 3 3 2
9.1.3.4 Structure of M O Br [SeO ] (M = La, Pr) and M O Cl [SeO ] (M = Pr, Nd, 9 8 3 3 4 9 8 3 3 4
Sm, Gd) 191
9.1.4 An alkali metal oxoselenate(IV) of a trivalent rare-earth-element: Li Lu [SeO ] 192 3 5 3 9
9.1.5 An alkali metal halide oxoselenate(IV) of a trivalent rare-earth-element:
CsTmCl [SeO] 193 2 3
9.1.6 An alkali metal oxide halide oxoselenate(IV) of a trivalent rare-earth-element:
CsEu O Cl [SeO ] 4 3 3 3 2
9.2 Outlook 194
10 Zusammenfassung und Ausblick 195
10.1 Ergebnisse 195
10.1.1 Oxoselenate(IV) der dreiwertigen Selten-Erd-Elemente 196
10.1.1.1 Das hexagonale Sc [SeO ] 196 2 3 3
10.1.1.2 Das orthorhombische Ce [SeO ] 197 2 3 3
10.1.1.3 Das monokline Pr [SeO ] 197 2 3 3
10.1.1.4 Das trikline M [SeO ] (M = Y, Sm – Lu) 198 2 3 3
10.1.2 Oxid-Oxoselenate(IV) der dreiwertigen Selten-Erd-Elemente 199
10.1.3 Oxidhalogenid-Oxoselenate(IV) der dreiwertig 200
10.1.3.1 Verbindungen der Formel M O Cl[SeO ] (M = Tb, Dy, Er) 2003 2 3 26 Table of contents
10.1.3.2 Verbindungen der Formel M O Cl [SeO ] (M = Er, Yb) 201 4 3 2 3 2
10.1.3.3 Struktur von Gd O Br [SeO ] und Tb O Cl [SeO ] 202 5 4 3 3 2 5 4 3 3 2
10.1.3.4 Struktur von M O Br [SeO ] (M = La, Pr) und M O Cl [SeO ] (M = Pr, Nd, 9 8 3 3 4 9 8 3 3 4
Sm, Gd) 203
10.1.4 Ein Alkalimetall-Oxoselenate(IV) mit dreiwertigem Selten-Erd-
Element: Li Lu [SeO ] 204 5 5 3 9
10.1.5 Ein Alkalimetall-Halogenide-Oxoselenate(IV) mit dreiwertigem Selten-Erd-
Element: CsTmCl [SeO] 204 2 3
10.1.6 Ein Alkalimetall-Oxihal