Porous Molecular Conductor: Electrochemical Fabrication of Through-Space Conduction Pathways among Linear Coordination Polymers

The
first porous molecular conductor (PMC), which exhibits porosity,
a through-space conduction pathway and rich charge carriers (electrons),
was prepared through electrocrystallization from Cd2+ and N,N′-di­(4-pyridyl)-1,4,5,8-naphthalenetetracarboxdiimide
(NDI-py). [Cd­(NDI-py)­(OH2)4]­(NO3)1.3±0.1·nDMA (PMC-1) was assembled by π–π stacking among one-dimensional
(1D) linear coordination polymers. The NDI cores were partially reduced
into radical anions to form conductive π-stacked columns, yielding
(1.0–3.3) × 10–3 S cm–1 at room temperature. Moreover, the electrical conductivity was significantly
enhanced by removing the solvent molecules from PMC-1, indicating that PMCs are promising as molecule-responsive conductive
materials.