The development of 2D electrically conductive metal− organic frameworks (EC-MOFs) has significantly expanded the scope of MOFs' applications into energy storage, electrocatalysis, and sensors. Despite growing interest in EC-MOFs, they often show low surface area and lack functionality due to the limited ligand motifs available. Herein we present a new EC-MOF using 2,3,8,9,14,15-hexahydroxyltribenzocyclyne (HHTC) linker and Cu nodes, featuring a large surface area. The MOF exhibits an electrical conductivity up to 3.02 × 10 −3 S/ cm and a surface area up to 1196 m 2 /g, unprecedentedly high for 2D EC-MOFs. We also demonstrate the utilization of alkyne functionality in the framework by postsynthetically hosting heterometal ions (e.g., Ni 2+ , Co 2+ ). Additionally, we investigated particle size tunability, facilitating the study of size−property relationships. We believe that these results not only contribute to expanding the library of EC-MOFs but shed light on the new opportunities to explore electronic applications.

The emergence of 2D electrically conductive metal–organic frameworks (MOFs) has significantly expanded the scope of metal–organic framework applications from electrochemical energy storage to electronic devices. However, their potentials are not fully exploited due to limited accessibility to internal pores in stacked 2D structures. Herein we transform a 2D conjugated MOF into a 3D framework via postsynthetic pillar-ligand insertion. Cu-THQ was chosen due to its ability to adopt additional ligands at the axial positions at the copper nodes. Cu-THQ demonstrates that structural augmentation increases ion accessibility into internal pores, resulting in an increased gravimetric capacitance up to double that of the pristine counterpart. Beyond this, we believe that our findings can further be used to functionalize the existing 2D conductive MOFs to offer more opportunities in sensing, electronic, and energy-related applications by utilizing additional functions and increased accessibility from the pillars.

A trisulfur-radical-anion (S3̇–)-triggered C­(sp2)–H amination of α,β-unsaturated carbonyl derivatives with simple amines has been demonstrated. This protocol provides convenient access to a variety of synthetically valuable N-unprotected and secondary β-enaminones with absolute Z selectivity and tertiary β-enaminones with E selectivity. Mechanistic probe and electronic structure theory calculations suggest that S3̇– initiates the nucleophilic attacks via a thiirane intermediate.