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The large-scale synthesis of high-quality thin films with extensive tunability derived from molecular building blocks will advance the development of artificial solids with designed functionalities. We report the synthesis of two-dimensional (2D) porphyrin polymer films with wafer-scale homogeneity in the ultimate limit of monolayer thickness by growing films at a sharp pentane/water interface, which allows the fabrication of their hybrid superlattices. Laminar assembly polymerization of porphyrin monomers could form monolayers of metal-organic frameworks with Cu 2+ linkers or covalent organic frameworks with terephthalaldehyde linkers. Both the lattice structures and optical properties of these 2D films were directly controlled by the molecular monomers and polymerization chemistries. The 2D polymers were used to fabricate arrays of hybrid superlattices with molybdenum disulfide that could be used in electrical capacitors. 

The emergence of conductive 2D and less commonly 3D coordination polymers (CPs) and metal–organic frameworks (MOFs) promises novel applications in many fields. However, the synthetic parameters for these electronically complex materials are not thoroughly understood. Here we report a new 3D semiconducting CPFe₅(C₆O₆)₃, which is a fusion of 2D Fe‐semiquinoid materials and 3D cubicFe_x(C₆O₆)_ymaterials, by using a different initial redox‐state of the C₆O₆linker. The material displays high electrical conductivity (0.02 S cm⁻¹), broad electronic transitions, promising thermoelectric behavior (S²σ=7.0×10⁻⁹ W m⁻¹ K⁻²), and strong antiferromagnetic interactions at room temperature. This material illustrates how controlling the oxidation states of redox‐active components in conducting CPs/MOFs can be a “pre‐synthetic” strategy to carefully tune material topologies and properties in contrast to more commonly encountered post‐synthetic modifications.

 

The emergence of conductive 2D and less commonly 3D coordination polymers (CPs) and metal–organic frameworks (MOFs) promises novel applications in many fields. However, the synthetic parameters for these electronically complex materials are not thoroughly understood. Here we report a new 3D semiconducting CPFe₅(C₆O₆)₃, which is a fusion of 2D Fe‐semiquinoid materials and 3D cubicFe_x(C₆O₆)_ymaterials, by using a different initial redox‐state of the C₆O₆linker. The material displays high electrical conductivity (0.02 S cm⁻¹), broad electronic transitions, promising thermoelectric behavior (S²σ=7.0×10⁻⁹ W m⁻¹ K⁻²), and strong antiferromagnetic interactions at room temperature. This material illustrates how controlling the oxidation states of redox‐active components in conducting CPs/MOFs can be a “pre‐synthetic” strategy to carefully tune material topologies and properties in contrast to more commonly encountered post‐synthetic modifications.