Host–Guest Interactions and Redox Activity in Layered Conductive Metal–Organic Frameworks

This paper describes the identification of specific host–guest interactions between basic gases (NH3, CD3CN, and pyridine) and four topologically similar 2-dimensional (2D) metal–organic frameworks (MOFs) comprising copper and nickel bis­(diimine) and bis­(dioxolene) linkages of triphenylene-based ligands using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy (EPR), and powder X-ray diffraction (PXRD). This contribution demonstrates that synthetic bottom-up control over surface chemistry of layered MOFs can be used to impart Lewis acidity or a mixture of Brønsted and Lewis acidities, through the choice of organic ligand and metal cation. This work also distinguishes differences in redox activity within this class of MOFs that contribute to their ability to promote electronic transduction of intermolecular interactions. Future design of structure–function relationships within multifunctional 2D MOFs will benefit from the insights this work provides.