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Abstract 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 Cu₃(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, Cu₃(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, Cu₃(HHTP)(HHTQ) exhibits higher bulk conductivity (0.12 S/m at 295 K) than single‐ligand MOFs Cu₃(HHTP)₂(7.3 × 10⁻²S/m) and Cu₃(HHTQ)₂(5.9 × 10⁻⁴S/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. 

Abstract Electrocatalytic hydrogen gas production is considered a potential pathway towards carbon‐neutral energy sources. However, the development of this technology is hindered by the lack of efficient, cost‐effective, and environmentally benign catalysts. In this study, a main‐group‐element‐based electrocatalyst,SbSalen, is reported to catalyze the hydrogen evolution reaction (HER) in an aqueous medium. The heterogenized molecular system achieved a Faradaic efficiency of 100 % at −1.4 V vs. NHE with a maximum current density of −30.7 mA/cm². X‐ray photoelectron spectroscopy of the catalyst‐bound working electrode before and after electrolysis confirmed the molecular stability during catalysis. The turnover frequency was calculated as 43.4 s⁻¹using redox‐peak integration. The kinetic and mechanistic aspects of the electrocatalytic reaction were further examined by computational methods. This study provides mechanistic insights into main‐group‐element electrocatalysts for heterogeneous small‐molecule conversion.