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.

Ammonium and sodium salts (ion pairs) of a multi-interactive tri(4-pyridyl)hexaazaphenalenyl anion (TPHAP(-)) showed completely different ion-conductive properties depending on the crystal structure. TPHAP columnar crystals showed a high conductivity of 10(-3) S cm(-1) while retaining their structures even under humid conditions, whereas TPHAP dimer crystals exhibited a conductivity of ∼10(-5) S cm(-1) with crystallinity deterioration. The main unit structures induced by multi-interactivity realized different water accessibility, which explains the differences in their ion conductivity and stability against humidity.

Crystalline powders self-assembled from interactive discrete molecules reversibly transformed from a porous structure to a 2D one with a nanometer-thick H2O layer by hydration/dehydration. Multi-point weak intermolecular interactions contributed to maintenance of each phase. This structure transformation induced a humidity-dependent ion conductivity change from insulator to 3.4 × 10(-3) S cm(-1).