Owing to their molecular building blocks, yet highly crystalline nature, metal−organic frameworks (MOFs) sit at the interface between molecule and material. Their diverse structures and compositions enable them to be useful materials as catalysts in heterogeneous reactions, electrical conductors in energy storage and transfer applications, chromophores in photoenabled chemical transformations, and beyond. In all cases, density functional theory (DFT) and higher-level methods for electronic structure determination provide valuable quantitative information about the electronic properties that underpin the functions of these frameworks. However, there are only two general modeling approaches in conventional electronic structure software packages: those that treat materials as extended, periodic solids, and those that treat materials as discrete molecules. Each approach has features and benefits; both have been widely employed to understand the emergent chemistry that arises from the formation of the metal−organic interface. This Review canvases these approaches to date, with emphasis placed on the application of electronic structure theory to explore reactivity and electron transfer using periodic, molecular, and embedded models. This includes (i) computational chemistry considerations such as how functional, k-grid, and other model variables are selected to enable insights into MOF properties, (ii) extended solid models that treat MOFs as materials rather than molecules, (iii) the mechanics of cluster extraction and subsequent chemistry enabled by these molecular models, (iv) catalytic studies using both solids and clusters thereof, and (v) embedded, mixed-method approaches, which simulate a fraction of the material using one level of theory and the remainder of the material using another dissimilar theoretical implementation.

Platinum­(II) compounds are a critical class of chemotherapeutic agents. Recent studies have highlighted the ability of a subset of Pt­(II) compounds, including oxaliplatin but not cisplatin, to induce cytotoxicity via nucleolar stress rather than a canonical DNA damage response. In this study, influential properties of Pt­(II) compounds were investigated using redistribution of nucleophosmin (NPM1) as a marker of nucleolar stress. NPM1 assays were coupled to calculated and measured properties such as compound size and hydrophobicity. The oxalate leaving group of oxaliplatin is not required for NPM1 redistribution. Interestingly, although changes in diaminocyclohexane (DACH) ligand ring size and aromaticity can be tolerated, ring orientation appears important for stress induction. The specificity of ligand requirements provides insight into the striking ability of only certain Pt­(II) compounds to activate nucleolar processes.

We identify the existence of nonlinear optical (NLO) activity in a number of novel ABX3-type metal-free perovskites, where A is a highly tuneable organic cation, B is a NH4 cation and X is a halide anion.