We synthesized a 2D crystalline open framework material that combines the porosity of a MOF with the redox properties of Co6Se8 clusters, the main components of the framework. Our building block of choice is a Co6Se8L6 superatom (SA), which has ligand tunability, multiple accessible redox states, and charge transport capabilities. We sought a rational construction of a superatom framework from a nanosized octahedral carboxylate six-node “ligand”, Co6Se8(PEt2PhCOOH)6, and zinc nitrate. We designed metal chalcogenide clusters with chemically active carboxylate ligands for framework formation, and then incorporated these building blocks into a covalent framework material. Single crystal X-ray diffraction studies revealed the structure of the SA framework, and the material was further characterized with powder XRD, SEM, AFM, and cyclic voltammetry (CV). The framework is composed of two-dimensional arrays of covalently bound neutral SAs and Zn2 clusters extended in three dimensions via a hydrogen-bonded network. CV of the material reveals multiple reversible redox events. Lastly, the framework can be exfoliated into ultrathin nanosheets. Atomic force microscopy shows a smooth nanosheet surface with a thickness of 2nm.

2D redox-active superatom frameworks

253rd National Meeting (2017)

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