One- and two-dimensional coordination networks of the tetracyanoethylene anion-radicals with potassium counter-ions

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.

Coordination of solvent molecules and/or crown-ether ligands to potassium cations modulates their binding with tetracyanoethylene anion-radical and results in crystallization of either 2-D networks (with unusual μ3-TCNE/K double chains tethered by THF bridges and TCNE π-bonding), 1-D coordination polymers or isolated anion-radicals in the separated ion pairs.Figure optionsDownload as PowerPoint slide