Impact of Metal-Ion Dependence on the Porous and Electronic Properties of TCNQ-Dianion-Based Porous Coordination Polymers

A series of TCNQ-dianion-based porous coordination polymers [M(TCNQ)bpy] (M = Fe, Zn, Mn, Co, Cd) have been synthesized and characterized. The synthesis reactions of these compounds are promoted by the addition of ascorbic acid, which is the key to obtaining a high yield. They form almost identical three-dimensional pillared layer structures with the M−TCNQ two-dimensional layers linked by bpy pillar ligands. The electronic properties of these compounds vary depending on the constitutional metal ions and guest molecules. We found that the electronic interaction between metal ions and TCNQ moieties in the frameworks strongly impacted the electronic properties of the compounds.