Single Crystals of Electrically Conductive Two-Dimensional Metal-Organic Frameworks: Structural and Electrical Transport Properties

Crystalline, electrically conductive, and intrinsically porous materials are rare. Layered two-dimensional (2D) metal-organic frameworks (MOFs) break this trend. They are porous crystals that exhibit high electrical conductivity and are novel platforms for studying fundamentals of electricity and magnetism in two dimensions. Despite demonstrated applications, electrical transport in these remains poorly understood because of a lack of single crystal studies. Here, studies of single crystals of two 2D MOFs, Ni-3(HITP)(2) and Cu-3(HHTP)(2), uncover critical insights into their structure and transport. Conductivity measurements down to 0.3 K suggest metallicity for mesoscopic single crystals of Ni-3(HITP)(2), which contrasts with apparent activated conductivity for polycrystalline films. Microscopy studies further reveal that these MOFs are not isostructural as previously reported. Notably, single rods exhibit conductivities up to 150 S/cm, which persist even after prolonged exposure to ambient conditions. These single crystal studies confirm that 2D MOFs hold promise as molecularly tunable platforms for fundamental science and applications where porosity and conductivity are critical.