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Controlling the Assembly of Chalcogenide Anions in Ionic Liquids: From Binary Ge/Se through Ternary Ge/Sn/Se to Binary Sn/Se Frameworks
Author(s) -
Lin Yumei,
Massa Werner,
Dehnen Stefanie
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201774
Subject(s) - ionic liquid , ternary operation , chalcogenide , amine gas treating , ionic bonding , crystallography , chemistry , materials science , inorganic chemistry , ion , organic chemistry , catalysis , computer science , programming language
Seven compounds with binary or ternary Ge/Se, Ge/Sn/Se, or Sn/Se anionic substructures crystallized upon the ionothermal reactions of [K 4 (H 2 O) 3 ][Ge 4 Se 10 ] with SnCl 4 ⋅ 5 H 2 O or SnCl 2 in [BMMIm][BF 4 ] or [BMIm][BF 4 ] (BMMIm=1‐butyl‐2,3‐dimethyl‐imidazolium, BMIm=1‐butyl‐3‐methyl‐imidazolium). The products were obtained by subtly varying the reaction conditions; the nature and amount of an additional amine was the most important parameter in the product selection and in determining the Sn/Ge ratio in the isolated products. The crystal structures of these chalcogenides were based on complex anions with unprecedented topologies that varied from discrete clusters (0D) through 1D chain structures or 2D layers to 3D frameworks. The architecture and composition of the title compounds were well reflected by their optical absorption behavior. Herein, we report a convenient approach for the generation of chalcogenidometallate phases with fine‐tunable electronic properties in ionic liquids, which have been inaccessible by traditional methods.