Ortho-Alkoxy-benzamide Directed Formation of a Single Crystalline Hydrogen-bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis.

Boron trifluoride (BF3 ) is a highly corrosive gas widely used in industry. Confining BF3 in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF3 corrosion. Herein, we designed and synthesized a Lewis basic single-crystalline hydrogen-bond crosslinked organic framework (HC OF-50) for BF3 storage and its application in catalysis. Specifically, we introduced self-complementary ortho-alkoxy-benzamide hydrogen-bonding moieties to direct the formation of highly organized hydrogen-bonded networks, which were subsequently photo-crosslinked to generate HC OFs. The HC OF-50 features Lewis basic thioether linkages and electron-rich pore surfaces for BF3 uptake. As a result, HC OF-50 shows a record-high 14.2 mmol/g BF3 uptake capacity. The BF3 uptake in HC OF-50 is reversible, leading to the slow release of BF3 . We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF3 ⋅ Et2 O. The elucidation of the structure-property relationship, as provided by the single-crystal X-ray structures, combined with the high BF3 uptake capacity and controlled sorption, highlights the molecular understanding of framework-guest interactions in addressing contemporary challenges.

Emissive Click Cages.

This study reports the synthesis of cofacial organic cage molecules containing aggregation-induced emissive (AIE) luminogens (AIEgens) through four-fold Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) "click" reactions. The shorter AIEgen, tetraphenylethylene (TPE), afforded two orientational isomers (TPE-CC-1A and TPE-CC-1B). The longer AIEgen, tetrabiphenylethylene (TBPE), afforded a single isomer (TBPE-CC-2). The click reaction employed is irreversible, yet it yielded remarkable four-fold click products above 40 %. The phenyl rings around the ethylene core generate propeller-shaped chirality owing to their orientation, which influences the chirality of the resulting cages. The shorter cages are a mixture of PP/MM isomers, while the longer ones are a mixture of PM/MP isomers, as evidenced by their x-ray structures. The newly synthesized cage molecules are emissive even in dilute solutions (THF) and exhibit enhanced AIE upon the addition of water. The aggregated cage molecules in aqueous solution exhibit turn-off emission sensing of nitroaromatic explosives, with selectivity to picric acid in the 25-38 nanomolar detection range.

Conformationally Flexible Cleft Receptor for Chloride Anion Transport.

The design and synthesis of a cleft-shaped bis-diarylurea receptor for chloride anion transport is reported in this work. The receptor is based on the foldameric nature of N,N'-diphenylurea upon its dimethylation. The bis-diarylurea receptor exhibits a strong and selective affinity for chloride over bromide and iodide anions. A nanomolar quantity of the receptor efficiently transports the chloride across a lipid bilayer membrane as a 1:1 complex (EC50 = 5.23 nm). The work demonstrates the utility of the N,N'-dimethyl-N,N'-diphenylurea scaffold in anion recognition and transport.

Chiral Self-Sorting in Pd6 L12 Metal-Organic Cages.

Chiral self-sorting during the formation of cage-like molecules continues to fascinate and advance our understanding of the phenomenon in general. Herein, we report the chiral self-sorting in the Pd6 L12 -type metal-organic cages. When a racemic mixture of axially chiral bis-pyridyl ligands undergo coordination-driven self-assembly with Pd(II) ions to form Pd6 L12 -type cages, the system has the option of chiral self-sorting to afford any of at least 70 pairs of (one homochiral and 69 heterochiral) enantiomers and 5 meso isomers or a statistical mixture of everything. However, the system resulted in diastereoselective self-assembly through a high-fidelity chiral social self-sorting to form a racemic mixture of D3 symmetric heterochiral [Pd6 (L6R/6S )12 ]12+ /[Pd6 (L6S/6R )12 ]12+ cages.

Overcoming the Deallylation Problem: Palladium(II)-Catalyzed Chemo-, Regio-, and Stereoselective Allylic Oxidation of Aryl Allyl Ether, Amine, and Amino Acids.

We report herein a Pd(II)/bis-sulfoxide-catalyzed intramolecular allylic C-H acetoxylation of aryl allyl ether, amine, and amino acids with the retention of a labile allyl moiety. Mechanistically, the reaction proceeds through a distinct double-bond isomerization from the allylic to the vinylic position followed by intramolecular carboxypalladation and the ß-hydride elimination pathway. For the first time, C-H oxidation of N-allyl-protected amino acids to furnish five-membered heterocycles through 1,3-syn-addition is established with excellent diastereoselectivity.

CNS activities of ethanol extract of aerial parts of Hygrophila difformis in mice.

The ethanol extract of aerial parts of Hygrophila difformis (EEHD) was tested for possible pharmacological effects on experimental animals. EEHD significantly potentiated the sleeping time of mice induced by standard hypnotics, viz. pentobarbital sodium, diazepam, and meprobamate in a dose dependent manner. EEHD showed significant analgesic properties as evidenced by the significant reduction in the number of writhes and stretches induced in mice by 1.2% acetic acid solution. It also potentiated analgesia induced by morphine and pethidine in mice. Pretreatment with EEHD caused significant protection against strychnine and leptazol-induced convulsions. The behavioral studies on mice indicate CNS depressant activity of the ethanol extract of H. difformis.