The first bio-inspired microporous metal-organic framework (MOF) synthesized using ellagic acid, a common natural anti-oxidant and polyphenol building unit, is presented. Bi₂O(H₂O)₂(C₁₄H₂O₈)·nH₂O (SU-101) was inspired by bismuth phenolate metallodrugs, and was synthesized entirely from non-hazardous or edible reagents under ambient aqueous conditions, ena-bling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid were sourced from tree bark and pomegranate hulls, respectively. Biocompatibility and colloidal stability were confirmed by in vitro assays. The material exhibits remarkable chemical stability for a bio-inspired MOF (pH = 2-14, hydrothermal conditions, heated organic solvents, biological media, SO₂ and H₂S), attributed to the strongly chelating phenolates. A total H₂S uptake of 15.95 mmol g-1 was recorded, representing one of the highest H₂S capacities for a MOF, where polysulfides are formed inside the pores of the material. Phenolic phytochemicals remain largely unexplored as linkers for MOF synthesis, opening new avenues to design stable, eco-friendly, scalable, and low-cost MOFs for diverse applications, including drug delivery.

Emerging organic contaminants (EOCs), such as pharmaceutical compounds, are of growing environmental concern, and there is a need to develop new materials and technologies for their efficient removal. Here we developed a highly porous and stable zirconium–ellagate framework, denoted SU-102, which was used to remove EOCs from water, including real municipal wastewater treatment plant effluent. SU-102 adsorbs cationic EOCs with particularly high efficiencies, and of the 17 pharmaceutical EOCs detected in wastewater treatment plant effluent, all 9 cationic species were removed with efficiencies of at least 79.0–99.6%, emphasizing the importance of framework charge on selectivity. As a second mechanism of EOC removal, SU-102 photodegraded the antibiotic sulphamethazine under visible light. SU-102 is synthesized from ellagic acid, an edible polyphenol building unit, highlighting the possibility of creating stable high-performance multi-functional materials from sustainably sourced plant-based components.

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO₂. Recently, metal–organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal–organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB₂OX₃ bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 mol_H2 g_cat.^–1 min^–1, a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10^–5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.

A molecular crystal of a 2-D hydrogen-bonded organic framework (HOF) undergoes an unusual structural transformation after solvent removal from the crystal pores during activation. The conformationally flexible host molecule, ABTPA, adapts its molecular conformation during activation to initiate a framework expansion. The microcrystalline activated phase was characterized by three-dimensional electron diffraction (3D ED), which revealed that ABTPA uses out-of-plane anthracene units as adaptive structural anchors. These units change orientation to generate an expanded, lower density framework material in the activated structure. The porous HOF, ABTPA-2, has robust dynamic porosity (SA_BET = 1183 m² g^–1) and exhibits negative area thermal expansion. We use crystal structure prediction (CSP) to understand the underlying energetics behind the structural transformation and discuss the challenges facing CSP for such flexible molecules.

Electron transport through metal–organic frameworks by a hopping mechanism between discrete redox active sites is coupled to diffusion-migration of charge-balancing counter cations. Experimentally determined apparent diffusion coefficients, D_e^app, that characterize this form of charge transport thus contain contributions from both processes. While this is well established for MOFs, microscopic descriptions of this process are largely lacking. Herein, we systematically lay out different scenarios for cation-coupled electron transfer processes that are at the heart of charge diffusion through MOFs. Through systematic variations of solvents and electrolyte cations, it is shown that the D_e^app for charge migration through a PIZOF-type MOF, Zr(dcphOH-NDI) that is composed of redox-active naphthalenediimide (NDI) linkers, spans over 2 orders of magnitude. More importantly, however, the microscopic mechanisms for cation-coupled electron propagation are contingent on differing factors depending on the size of the cation and its propensity to engage in ion pairs with reduced linkers, either non-specifically or in defined structural arrangements. Based on computations and in agreement with experimental results, we show that ion pairing generally has an adverse effect on cation transport, thereby slowing down charge transport. In Zr(dcphOH-NDI), however, specific cation–linker interactions can open pathways for concerted cation-coupled electron transfer processes that can outcompete limitations from reduced cation flux.

Designing polymeric materials for closed-loop material streams is the key to achieving a circular society. Here, a library of macrocyclic carbonates (MCs) was designed by a facile and direct one-pot, two-step synthesis approach without the use of a solvent at a 10 g scale. We demonstrate that anionic polymerization with tert-butoxide enables the ultrafast ring-opening polymerization (ROP) of MCs with high conversion (>97%) within seconds (3–10 s) at ambient temperature. The polymerization rate depends on the odd or even number of methylene groups between the carbonate linkages in the MCs, and not the overall ring size, yielding an “odd–even” effect. This polymerization rate is related to the difference in molecular conformation of the MCs, as determined by X-ray crystallography. The polymers (polypenta-, hexa-, heptamethylene carbonate) were subsequently regenerated back to their original MCs at a high selectivity (95–99 mol %) and good yields (70–85%), hence taking a step toward closing the loop on these long alkyl chain polycarbonates.