A new approach to TCNQ-Based coordination polymers via TCNQH2

2,2'-(p-Phenylene)bis(propanedinitrile), (NC)(2)CH center dot C6H4 center dot CH(CN)(2) (referred to as TCNQH(2)), upon reaction with Cd(NO3)(2), [(C6H5)(3)PMe]Br, and Li(CH3CO2) in MeOH/DMF at room temperature in air yields an air-stable product of composition (Ph3PMe)(2)[Cd-2(TCNQ)(3)] in the form of rhombohedral single crystals amenable to X-ray diffraction studies. In the anionic three-dimensional (3D) {[Cd-2(TCNQ)(3)](2-))(infinity) coordination network Cd centers are in an approximately octahedral coordination environment consisting of N atoms from six TCNQ 2- units each of which is in turn attached to four Cd 21 centers at the corners of a quadrilateral that is almost a square. The disposition of the Cd centers is only very slightly distorted from primitive cubic. The results constitute a "proof of concept" for our proposition that easily accessible, air-stable TCNQH(2) may afford a very convenient general entry into new types of coordination polymers based on the TCNQ(2-) anion and that these in turn may be amenable to redox intercalation to afford materials in which TCNQ is present either as the TCNQ(-) radical or in mixed oxidation states.