Electrically Conducting Redox‐Complementary Dual‐Ligand 2D Graphitic MOF with Orthogonal Charge Transport Pathways

Due to their diverse potential in advanced electronics and energy technologies, electrically conducting metal‐organic frameworks (MOFs) are drawing significant attention. Although hexagonal 2D MOFs generally display impressive electrical conductivity because of their dual in‐plane (through bonds) and out‐of‐plane (through π‐stacked ligands) charge transport pathways, notable differences between these two orthogonal conduction routes cause anisotropic conductivity and lower bulk conductivity. To address this issue, we have developed the first redox‐complementary dual‐ligand 2D MOF Cu 3 (HHTP)(HHTQ), featuring a π‐donor hexahydroxytriphenylene (HHTP) ligand and a π‐acceptor hexahydroxytricycloquinazoline (HHTQ) ligand located at alternate corners of the hexagons, which form either parallel HHTP and HHTQ stacks (AA stacking) or alternating HHTP/HHTQ stacks (AB stacking) along the c‐axis. Regardless of the stacking pattern, Cu 3 (HHTP)(HHTQ) supports more effective out‐of‐plane conduction through either separate π‐donor and π‐acceptor stacks or alternating π‐donor/acceptor stacks, while promoting in‐plane conduction through the pushpull‐like heteroleptic coordination network. As a result, Cu 3 (HHTP)(HHTQ) exhibits higher bulk conductivity (0.12 S/m at 295 K) than single‐ligand MOFs Cu 3 (HHTP) 2 (7.3 × 10 −2 S/m) and Cu 3 (HHTQ) 2 (5.9 × 10 −4 S/m). This work introduces a new design approach to improve the bulk electrical conductivity of 2D MOFs by supporting charge transport in both in‐ and out‐of‐plane direcations.