The first bioinspired microporous metal–organic framework (MOF) synthesized using ellagic acid, a common natural antioxidant and polyphenol building unit, is presented. Bi 2 O(H 2 O) 2 (C 14 H 2 O 8 )· n H 2 O (SU-101) was inspired by bismuth phenolate metallodrugs, and could be synthesized entirely from nonhazardous or edible reagents under ambient aqueous conditions, enabling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid was 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 bioinspired MOF (pH = 2–14, hydrothermal conditions, heated organic solvents, biological media, SO 2 and H 2 S), attributed to the strongly chelating phenolates. A total H 2 S uptake of 15.95 mmol g –1 was recorded, representing one of the highest H 2 S 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.

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A new porous titanium(IV) squarate metal–organic framework (MOF), denoted as IEF‐11, having a never reported titanium secondary building unit, is successfully synthesized and fully characterized. IEF‐11 not only exhibits a permanent porosity but also an outstanding chemical stability. Further, as a consequence of combining the photoactive Ti(IV) and the electroactive squarate, IEF‐11 presents relevant optoelectronic properties, applied here to the photocatalytic overall water splitting reaction. Remarkably, IEF‐11 as a photocatalyst is able to produce record H2 amounts for MOF‐based materials under simulated sunlight (up to 672 µmol gcatalyst in 22 h) without any activity loss during at least 10 d.

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 m 2 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.

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.