Among the different alternatives for catalysis using metal–organic frameworks (MOFs) or covalent organic frameworks (COFs), photocatalysis has remarkably evolved during the last decade. Photocatalytic reticular materials allowed recyclability and easy separation of catalyst from the product, also reaching the activity and selectivity commonly observed for molecular systems. Recently, photocatalytic MOFs and COFs have been applied to synthetic applications in order to obtain organic molecules of different complexity. However, although a good number of works have been devoted to this issue, an updated comprehensive revision on this field is still needed. The aim of this review was to fill this gap covering the following three general aspects: (1) common strategies on the design of reticular photocatalytic materials, (2) a comprehensive discussion of the photocatalytic organic reactions achieved by the use of COFs and MOFs, and (3) some critical considerations highlighting directions that should be considered in order to make advances in the study of photocatalytic COFs and MOFs.

A well-established strategy to synthesize heterogeneous, metal-organic framework (MOF) catalysts that exhibit nanoconfinement effects, and specific pores with highly-localized catalytic sites, is to use organic linkers containing organocatalytic centers. Here, we report that by combining this linker approach with reticular chemistry, and exploiting three-dimensioanl (3D) MOF-structural data from the Cambridge Structural Database, we have designed four heterogeneous MOF-based catalysts for standard organic transformations. These programmable MOFs are isoreticular versions of pcu IRMOF-16, fcu UiO-68 and pillared-pcu SNU-8X, the three most common topologies of MOFs built from the organic linker p,p’-terphenyldicarboxylic acid (tpdc). To synthesize the four squaramide-based MOFs, we designed and synthesized a linker, 4,4’-((3,4‐dioxocyclobut‐1‐ene‐1,2‐diyl)bis(azanedyil))dibenzoic acid (Sq_tpdc), which is identical in directionality and length to tpdc but which contains organocatalytic squaramide centers. Squaramides were chosen because their immobilization into a framework enhances its reactivity and stability while avoiding any self-quenching phenomena. Therefore, the four MOFs share the same organocatalytic squaramide moiety, but confine it within distinct pore environments. We then evaluated these MOFs as heterogeneous H-bonding catalysts in organic transformations: a Friedel-Crafts alkylation and an epoxide ring-opening. Some of them exhibited good performance in both reactions but all showed distinct catalytic profiles that reflect their structural differences.

A set of OER electrodes based on Co(OH) ₂ nanoparticles and carbon microfibers of tailored composition is reported, which allows extracting valuable insights on the influence of the metal-support interface in their electrocatalytic performance.

Reaction between concentrated solutions of phenotiazine containing trialdehyde building block 4,4′,4″-(10-phenothiazine-3,7,10-triyl)tribenzaldehyde and (1R,2R)-cyclohexane-1,2-diamine results in the formation of a yellow transparent film. Exhaustive characterization of this material indicates that it is the result of the assembly of a linear polymer resulting from the linking of imine-based macrocycles. Phenotiazine units confer to this plastic the optical properties characteristic of photocatalytic materials. The transparency of the obtained material enabled the performance of solvent-free photocatalytic processes. This concept is illustrated by the oxidation of liquid organic sulfides, which can be performed in a recyclable manner. According to selective quenching experiments, such processes are the result of the energy transfer to oxygen molecule, generating singlet oxygen that is able to activate the sulfide molecules directly.