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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Poly-pnictogen bonding: trapping halide ions by a tetradentate antimony(iii) Lewis acid
J Louis Beckmann1, Jonas Krieft1, Yury V Vishnevskiy1
1Chair of Inorganic and Structural Chemistry, Center for Molecular Materials CM2 Faculty of Chemistry, Bielefeld University Universitätsstrasse 25 Bielefeld 33615 Germany mitzel@uni-bielefeld.de.
Abstract:
A highly halide affine, tetradentate pnictogen-bonding host-system based on the syn-photodimer of 1,8-diethynylanthracene was synthesized by a selective tin-antimony exchange reaction. The host carries four C[triple bond, length as m-dash]C-Sb(C2F5)2 units and has been investigated regarding its ability to act as a Lewis acidic host component for the cooperative trapping of halide ions (F-, Cl-, Br-, I-). The chelating effect makes this host-system superior to its bidentate derivative in competition experiments. It represents a charge-reversed crown-4 and has the ability to dissolve otherwise poorly soluble salts like tetra-methyl-ammonium chloride. Its NMR-spectroscopic properties make it a potential probe for halide ions in solution. Insights into the structural properties of the halide adducts by X-ray diffraction and computational methods (DFT, QTAIM, IQA) reveal a complex interplay of attractive pnictogen bonding interactions and Coulomb repulsion.
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