Selective Formation of Conductive Network by Radical-Induced Oxidation

Abstract

Cd-based coordination networks having channels were formed selectively by using a redox-active aromatic ligand 2,5,8-tri(4-pyridyl)1,3-diazaphenalene (TPDAP, H+1-). An electron-conductive network having a π-π stacking columnar structure of TPDAP formed in the presence of a trace amount of TPDAP radical (1•). In contrast, a nonconductive network having a dimer unit of H+1- formed in the absence of 1•. These results suggest the presence of a unique oxidation mechanism of TPDAP induced by formation of H+1--1• dimer, which was initiated by a trace amount of 1•. The dimerization increased HOMO level of H+1- moiety within the dimer to generate further radicals that could not form when H+1- was well isolated in CH3OH. © 2016 American Chemical Society