Porous materials with open metal sites have been investigated to separate various gas mixtures.H owever,o pen metal sites showt he limitation in the separation of some challenging gas mixtures,s uch as C 2 H 2 /CO 2 .H erein, we propose an ew type of ultra-strong C 2 H 2 nano-trap based on multiple binding interactions to efficiently capture C 2 H 2 molecules and separate C 2 H 2 /CO 2 mixture.T he ultra-strong acetylene nano-trap shows ab enchmark Q st of 79.1 kJ mol À1 for C 2 H 2 ,arecordh igh pure C 2 H 2 uptake of 2.54 mmol g À1 at 1 10 À2 bar,a nd the highest C 2 H 2 /CO 2 selectivity (53.6), making it as an ew benchmark material for the capture of C 2 H 2 and the separation of C 2 H 2 /CO 2 .T he locations of C 2 H 2 molecules within the MOF-based nanotrap have been visualized by the in situ single-crystal X-ray diffraction studies,which also identify the multiple binding sites accountable for the strong interactions with C 2 H 2 .

The separation of xylene isomers (para-, meta-, orth-) remains a great challenge in the petrochemical industry due to their similar molecular structure and physical properties. Porous materials with sensitive nanospace and selective binding sites for discriminating the subtle structural difference of isomers are urgently needed. Here, we demonstrate the adaptively molecular discrimination of xylene isomers by employing a NbOF52−-pillared metal–organic framework (NbOFFIVE-bpy-Ni, also referred to as ZU-61) with rotational anionic sites. Single crystal X-ray diffraction studies indicate that ZU-61 with guest-responsive nanospace/sites can adapt the shape of specific isomers through geometric deformation and/or the rotation of fluorine atoms in anionic sites, thereby enabling ZU-61 to effectively differentiate xylene isomers through multiple C–H···F interactions. ZU-61 exhibited both high meta-xylene uptake capacity (3.4 mmol g−1) and meta-xylene/para-xylene separation selectivity (2.9, obtained from breakthrough curves), as well as a favorable separation sequence as confirmed by breakthrough experiments: para-xylene elute first with high-purity (≥99.9%), then meta-xylene, and orth-xylene. Such a remarkable performance of ZU-61 can be attributed to the type anionic binding sites together with its guest-response properties.

The corrole unit from the porphyrinoid family represents one of the most important ligands in the field of coordination chemistry, which creates a unique environment allowing for the observation of unusual electronic states of bound metal cations and has shown great promise in various applications. Nevertheless, studies that directly and systematically introduce these motifs in porous crystalline materials for targeting further functionalizations are still lacking. Herein, we report for the first time the construction of two robust corrole-based metal–organic frameworks (MOFs), M6(μ3-O)4­(μ3-OH)4­(OH)3­(H2O)3­(H3TCPC)3 (M = Zr for Corrole-MOF-1 and M = Hf for Corrole-MOF-2, H3TCPC = 5,10,15-tris­(p-carboxylphenyl)­corrole), which are assembled by a custom-designed C 2ν -symmetric corrolic tricarboxylate ligand and the unprecedented D 3d -symmetric 9-connected Zr6/Hf6 clusters. The resultant frameworks feature a rare (3,9)-connected gfy net and exhibit high chemical stability in aqueous solutions within a wide range of pH values. Furthermore, we successfully prepared the cationic Corrole-MOF-1­(Fe) from the iron corrole ligand, which can serve as an efficient heterogeneous catalyst for [4 + 2] hetero-Diels–Alder reactions between unactivated aldehydes and a simple diene, outperforming both the homogeneous counterpart and the porphyrinic MOF counterpart.

Herein, for the first time, we present the successful synthesis of a novel two‐dimensional corrole‐based covalent organic framework (COF) by reacting the unusual approximately T‐shaped 5,10,15‐tris(p‐aminophenyl)corrole H3TPAPC with terephthalaldehyde, which adopts desymmetrized hcb topology and consists of a staggered AB stacking structure with elliptical pores. The resultant corrole‐based COF, TPAPC‐COF, exhibits high crystallinity and excellent chemical stability. The combination of extended π‐conjugated backbone and interlayer noncovalent π–π interactions endows TPAPC‐COF with excellent absorption capability in the entire visible‐light and even near‐infrared regions. Moreover, this work suggests the promise of TPAPC‐COF as a new class of photoactive material for efficient singlet‐oxygen generation with potential photodynamic therapy application as demonstrated by in vitro anticancer studies.

Due to the high oxidation potential between AuI and AuIII, gold redox catalysis requires at least stoichiometric amounts of a strong oxidant. We herein report the first example of an electrochemical approach in promoting gold‐catalyzed oxidative coupling of terminal alkynes. Oxidation of AuI to AuIII was successfully achieved through anode oxidation, which enabled facile access to either symmetrical or unsymmetrical conjugated diynes through homo‐coupling or cross‐coupling. This report extends the reaction scope of this transformation to substrates that are not compatible with strong chemical oxidants and potentiates the versatility of gold redox chemistry through the utilization of electrochemical oxidative conditions.

In this report, we describe the synthesis of two porphyrin-containing Pt­(II) supramolecular assemblies via coordination-driven self-assembly. X-ray crystallographic analysis on one assembly reveals that the metalla-assembly formation imposes large interchromophore distances, leading to a higher 1O2 generation efficiency, relative to the corresponding small molecular precursors. The metalla-assemblies were examined as photosensitizers for photodynamic therapy as the potential reduction of the unfavorable self-aggregation phenomenon. In vivo and in vitro investigations demonstrate that the metalla-assemblies exhibit enhanced anticancer activity with minimal dose requirement and side effects comparable to the small molecule precursors. Thus, our work demonstrates that self-assembly provides a promising methodology for enhancing the therapeutic effectiveness of anticancer agents.

To offset the environmental impact of platinumgroup element (PGE) mining, recycling techniques are being explored. Porous organic polymers (POPs) have shown significant promise owing to their selectivity and ability to withstand harsh conditions. A series of pyridine-based POP nanotraps, POPPy , POP-pNH 2-Py, and POP-oNH 2-Py, have been designed and systematically explored for the capture of palladium, one of the most utilized PGEs. All of the POP nanotraps demonstrated record uptakes and rapid capture, with the amino group shown to be vital in improving performance. Further testing on the POP nanotrap regeneration and selectivity found that POP-oNH 2-Py outperformed POP-pNH 2-Py. Single-crystal X-ray analysis indicated that POP-oNH 2-Py provided a stronger complex compared to POP-pNH 2-Py owing to the intramolecular hydrogen bonding between the amino group and coordinated chlorine molecules. These results demonstrate how slight modifications to adsorbents can maximize their performance. Platinum-group elements (PGEs) are recognized for their unique properties such as corrosion resistance, high melting point, and catalytic qualities. These features have made them economically invaluable, with widespread use in a variety of industrial sectors. Elements in this category, namely platinum, palladium, rhodium, ruthenium, iridium, and osmium, are

Various robust, crystalline, and porous organic frameworks based on in situ‐formed imine‐linked oligomers were investigated. These oligomers self‐assembled through collaborative intermolecular hydrogen bonding interactions via liquid–liquid interfacial reactions. The soluble oligomers were kinetic products with multiple unreacted aldehyde groups that acted as hydrogen bond donors and acceptors and directed the assembly of the resulting oligomers into 3D frameworks. The sequential formation of robust covalent linkages and highly reversible hydrogen bonds enforced long‐range symmetry and facilitated the production of large single crystals, with structures that were unambiguously determined by single‐crystal X‐ray diffraction. The unique hierarchical arrangements increased the steric hindrance of the imine bond, which prevented attacks from water molecules, greatly improving the stability. The multiple binding sites in the frameworks enabled rapid sequestration of micropollutant in water.