Controlled Synthesis of Polyions of Heavy Main-Group Elements in Ionic Liquids

Abstract

Ionic liquids (ILs) have been proven to be valuable reaction media for the synthesis of inorganic materials among an abundance of other applications in different fields of chemistry. Up to now, the syntheses have remained mostly “black boxes”; and researchers have to resort to trial-and-error in order to establish a new synthetic route to a specific compound. This review comprises decisive reaction parameters and techniques for the directed synthesis of polyions of heavy main-group elements (fourth period and beyond) in ILs. Several families of compounds are presented ranging from polyhalides over carbonyl complexes and selenidostannates to homo and heteropolycations.

Lewis Acidic Ionic Liquids

“…Structural diversity of antimony-selenium heteropolycations accessible in haloaluminate(III) ILs under various reaction conditions[30] …”

The Subbromide Bi5Br4 – On the Existence of a Hidden Phase

“…Today, the polyhedral polycations Bi 5 + ,, Bi 5 3+ , Bi 6 2+ ,, Bi 8 2+ , Bi 9 5+ ,, and Bi 10 4+[23–38] are known, either as homoatomic entities or as parts of bismuth‐rich intermetalloid clusters additionally including electron‐rich transition metal atoms. This provided the basis for a detailed understanding of the structural and bonding principles in such clusters …”

The Role of [BF4]− and [B(CN)4]− Anions in the Ionothermal Synthesis of Chalcogenidometalates

“…According reactions start out from either the respective elements, from binary chalcogenides, or from binary or ternary chalcogidometalate precursor salts, and they are usually carried out under addition of auxiliary amines. The product structures are based on polyanionic clusters or networks with different dimensionalities (1D strands, 2D layers, or 3D networks) …”