Large Single Crystals of Two-Dimensional π-Conjugated Metal-Organic Frameworks via Biphasic Solution-Solid Growth.

Two-dimensional (2D) π-conjugated metal-organic frameworks (πMOFs) are a new class of designer electronic materials that are porous and tunable through the constituent organic molecules and choice of metal ions. Unlike typical MOFs, 2D πMOFs exhibit high conductivity mediated by delocalized π-electrons and have promising applications in a range of electrical devices as well as exotic physical properties. Here, we develop a growth method that generates single-crystal plates with lateral dimensions exceeding 10 μm, orders of magnitude bigger than previous methods. Synthesis of large single crystals eliminates a significant impediment to the fundamental characterization of the materials, allowing determination of the intrinsic conductivity and mobility along the 2D plane of πMOFs. A representative 2D πMOF, Ni-CAT-1, exhibits a conductivity of up to 2 S/cm, and Hall measurement reveals the origin of the high conductivity. Characterization of crystalline 2D πMOFs creates the foundation for developing electronic applications of this promising and highly diverse class of materials.