The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials is isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use High-Throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability and porosity, all relevant to photocatalysis. We use solvent assisted linker exchange reactions to produce a family of UiO-68-TZDC% binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution controls the distribution of this linker in the sibling crystals for a random mixture or the formation of core-shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical bandgap of the solids but controls their performance for drastic changes in the photocatalytic activity towards proton or methyl viologen reduction.

A high degree of crystallinity is an essential aspect in two-dimensional covalent organic frameworks, as many properties depend strongly on the structural arrangement of the different layers and their constituents. We introduce herein a new design strategy based on core-twisted polycyclic aromatic hydrocarbon as rigid nodes that give rise to a two-dimensional covalent organic framework with a wavy honeycomb (chair-like) lattice. The concave-convex self-complementarity of the wavy two-dimensional lattice guides the stacking of framework layers into a highly stable and ordered covalent organic framework that allows a full 3D analysis by transmission electron microscopy revealing its chair-like honeycomb facets and aligned mesoporous channels. Remarkably, the waviness of the framework does not disrupt the interlayer π-π stacking that shows charge transporting properties similar to those of planar covalent organic frameworks. The implementation of core-twisted aromatics as building blocks for covalent organic frameworks brings new possibilities in the design of highly ordered organic materials.

Three-dimensional covalent organic frameworks (3D COFs) with a pcu topology have been obtained from distorted polycyclic aromatic hydrocarbons acting as triangular antiprismatic (D 3d ) nodes. Such 3D COFs are six-fold interpenetrated as the result of interframework p-stacking, which enable charge transport properties that are not expected for 3D COFs.