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.