In-Plane Oriented Two-Dimensional Conjugated Metal–Organic Framework Films for High-Performance Humidity Sensing

Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) have emerged as a new generation of conducting MOFs for electronics. However, controlled synthesis of thin-film samples with high crystallinity and defined layer orientation, which is beneficial for achieving high-performance devices and reliable structure–property relationship, has remained a challenge. Here, we develop a surfactant-directed two-step synthesis of layered 2D c-MOF films based on benzene and triphenylene ligands linked by copper-bis­(diimino) complexes (HIB-Cu and HITP-Cu, respectively). The achieved layered 2D c-MOF films are featured as free-standing, in-plane oriented, and polycrystalline films with domain size up to ∼8000 nm² and a tunable thickness in the range of 8–340 nm. Benefiting from the intrinsic electrical conductivity and quasi-one-dimensional pore channels, a HIB-Cu film based chemiresistive sensor is constructed, displaying effective humidity sensing with a response as fast as ∼21 s, superior to the reported MOF-powder-based chemiresistive sensors (in the orders of minutes).