Inorganic Solid State Chemistry
Common building principles in solids: Introduction to materials sciences: definitions and characteristics, life-cycles of materials. General principles of structure chemistry: coordination number, coordination polyhedra, crystal systems and unit cell, atom coordination and projection of crystal structures, lattice types, Bravais lattices.
Fundamental crystal structures: Closely packed structures- space centred and primitive structures, crystalline solids, ionic solids of the composition MX and MX2, additional crystal structures; ionic and covalent radii, covalent and molecular crystals. Lattice energy: the Born-Haber-cycle, calculation of lattice energy, thermo-chemical cycle.
Principles of polyedra coupling: corner-shared octahedral, edge-shared octahedral, vertices-shared octahedral, octahedral with sharing corners and edges, octahedral with sharing edges and vertices, linked trigonal prisms, corner sharing tetrahedral (silicates and zeolites), edge sharing tetrahedra.
Bonding systems in solids: the band model: electrical, thermal and optical properties of metals, intrinsic and doped semi-conductors, energy bands in solid compounds.
Phase diagrams/polymorphism: Polymorphism –definition, classification, investigation, temperature dependency of phase equilibria, single/multi-component systems, high and low temperature phases, dynamic thermal analysis.
Synthesis methods: the real solid and its reactivity, reactions at elevated temperatures, grow of single crystals, precursor-, precipitation- and sol-gel-methods, closed reaction system and special gas atmospheres, crystallisation from solutions and hydrothermal synthesis, low temperature synthesis.
Defects and non-stoichiometry: defects and their concentration, ionic conductivity in solids, solid electrolytes, colour centres, non-stoichiometric compounds, two and three dimensional defects.
Zeolites and related structures: composition and structure, synthesis and structural refinement of zeolites, application of zeolites, real network structures.
A.R. West,G.: "Grundlagen der
Festkörperchemie“ VCH, 1992.
U. Müller: "Inorganic Structural Chemistry”, Wiley-VCH, 1994.
L. Smart, E. Moore: "Solid State Chemistry", Chapman & Hall
1996.
V. Boldyrev, K. Meyer: “Festkörperchemie” Dt. Verlag
Grundstoffindustre, 1973.
Advanced Main Group Chemistry
Inorganic Polymers
Historical Background, Definitions, Classifications:Classification of polymers according to different criteria: homo- and heteronuclear polymers; synthetic procedures; structural groups.
Characterization of Inorganic Polymers: Molecular weights and MW distributions; structural features; configuration-dependent properties; solubilities; transitions; glass transition temperature; mechanical properties.
Syntheses of Inorganic Polymers: - Condensation reactions at elevated temperatures: course of condensation processes in phosphates and silicates; influences of metal cations on the polyanions formed (network modifiers). - Addition polymerizations: the cases of sulfur and selenium; phosphorus-nitrogen compounds. Reactive species featuring multiple bonds as starting materials for cyclomerizations and polymerizations. - Formation of aggregates of cationic and anionic species in solution (coordination polymers, and silicates, borates, resp. in aqueous systems).
Homonuclear Polymers - Polycations, polyanions, neutral polymeric species: - Polysilanes by reduction of dichlorosilanes with alkali metals; disilene and silylene polymerization; dehydrogenative couplings; chemical and physical properties. - Polyphosphanes, polyorganophosphanes, polymeric phosphides featuring isolated anions; Zintl phases. - Linear and cyclic sulfur and selenium polymers: sulfur and its allotropes / modifications, comparison with selenium; polysulfanes, polyorganosulfanes; polysulfides; complex transition metal sulfides.
Heteronuclear Polymers: - Aluminum-oxygen- and aluminum-nitrogen-polymers: alumoxanes, aluminum oxide fibers; aluminum phosphate, aluminum nitride. - Boron-oxygen polymers (boric acid, borates), boron-carbon and boron-nitrogen polymers (carbaboranes, amino boranes, boron nitride). - Silicon-oxygen polymers: silicates (chain-, ribbon-, layer-, and spatial network-like silicates, modifications of silicon dioxide); zeolithes; polysiloxanes (synthesis of the monomers, ring opening polymerization, co-polymerization, structures and properties). - Silicon-nitrogen and silicon-carbon polymers: cyclo- and polysilazanes; carbosilanes. - Polymeric phosphates: formation, structures, properties, applications. - Polyphosphazenes: synthetic routes, structure, specifics of the P-N-bond; structure-property-relations. film and fiber-forming polyphosphazenes; specially substituted polyphosphazenes (organometallic, carbon and sulfur in the backbone etc.). - Sulfur-nitrogen polymers: chains, rings, cages: poly-(sulfur nitrides), structure and physical properties of poly-thiazyl.
Coordination polymers: - Principles of coordination polymer formation, classes of coordination polymers (one-, two- and three-dimensionally linked units). - Halogenides of transition group and platinum metals; fluorometallates. - Polymeric carboxylates and dithiocarbamates. - Polymeric phosphinates and dihalogenophosphates
Practical Applications of Inorganic Polymers: - High production volume polymers: cement and concrete. Synthetic inorganic fibers. Inorganic ion exchange polymers. Catalysts.
– Specialities and high-tech products, medical applications: polyphosphazenes, oxide and nitride based materials; composite materials.
F.G.A. Stone, W.A.G. Graham, Eds.:
"Inorganic Polymers", Academic Press, New York, London 1962.
F.G.R. Gimblett: "Inorganic Polymer Chemistry", Butterworths, London
1963.
N.H. Ray: "Inorganic Polymers", Academic Press, London, New York
1978.
J.E. Mark, H.R. Allcock, R. West: "Inorganic Polymers", Prentice Hall,
New Jersey 1992.
R.D. Archer: "Inorganic and Organometallic Polymers", Wiley-VCH
2001.