Abstract :
The article reports the selective formation of Cd-based coordination networks having channels by using a redox-active aromatic ligand 2,5,8-tri(4-pyridyl)1,3-diazaphenalene (TPDAP, H+1u). In the presence of a trace amount of TPDAP radical (1o) an electron-conductive network having a piupi stacking columnar structure of TPDAP formed; on the contrary, a nonconductive network having a dimer unit of H+1u formed when 1o was absent. These results implied the presence of a unique oxidation mechanism of TPDAP induced by formation of H+1u-1o dimer, which was initiated by a trace amount of 1o.