One- and two-dimensional coordination networks of the tetracyanoethylene anion-radicals with potassium counter-ions |
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Authors: | Sergiy V. Rosokha Bernd Lorenz Tetyana Y. Rosokha Jay K. Kochi |
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Affiliation: | 1. Department of Biological, Chemical and Physical Sciences, Roosevelt University, 430 S. Michigan Ave., Chicago, IL 60605, USA;2. Department of Chemistry, University of Houston, 4800 Calhoun Rd., Houston, TX 77204, USA;3. Department of Physics and Texas Center for Superconductivity, University of Houston, Houston, TX, USA |
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Abstract: | Potassium-mirror reduction of tetracyanoethylene (TCNE) acceptor in tetrahydrofuran affords K(THF)2 TCNE salt (1) showing double TCNE/K chains assembled via unusual μ3-TCNE-bridging of potassium cations. These parallel ladder-type chains are further tethered by pairs of THF bridges between potassium centers and by intermolecular π-bonding in (TCNE)22? dimers, and this results in formation of quasi-2-D coordination networks. In the presence of crown-ether ligand, the same potassium-mirror reduction lead to formation of [K(18-crown-6)(THF)2]TCNE salt (2) in which monomeric tetracyanoethylene anion-radicals are positioned between bulky [K+(18-crown-6)(THF)2] counter-ions. In comparison, crystallization of tetracyanoethylene anion-radicals with K+(18-crown-6) counter-ions in dichloromethane affords K(18-crown-6)TCNE salt (3) consisting of 1-D chains with 1,2-(N,N’)-TCNE bindings of potassium cations (nested in the crown-ether cavities). Temperature-dependent magnetic susceptibility study revealed essentially isolated tetracyanoethylene anion-radicals (S = 1/2) in this 1-D coordination polymer. |
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