Photoinduced C(sp3)–H chlorination of amides with tetrabutyl ammonium chloride

A new protocol was developed for the site-selective C(sp3)−H chlorination of amides with tetrabutyl ammonium chloride as the chlorinating agent. The reaction features a tandem sequence which involves a (diacetoxyiodo)benzene-mediated...

Tailoring the Diameters of Electro-Mechanically Spun Fibers by Controlling Their Deborah Numbers

Polymer solutions with different concentrations of SU-8 2002/poly(ethylene) glycol/tetrabutyl ammonium tetrafluoroborate (SU-8/PEO/TBATFB) were electrospun in a low-voltage near-field electrospinning platform (LVNFES) at different velocities. Their diameters were related to the concentration contents as well as to their Deborah (De) numbers, which describes the elasticity of the polymer solution under determined operating conditions. We found a direct correlation between the concentration of PEO/TBATFB, the De and the diameter of the fibers. Fibers with diameters as thin as 465 nm can be achieved for De ≈ 1.

TBAB-Catalyzed 1,6-Conjugate Sulfonylation of para-Quinone Methides: A Highly Efficient Approach to Unsymmetrical gem-Diarylmethyl Sulfones in Water

A highly efficient sulfonylation of para-quinone methides with sulfonyl hydrazines in water has been developed on the basis of the mode involving a tetrabutyl ammonium bromide (TBAB)-promoted sulfa-1,6-conjugated addition pathway. This reaction provides a green and sustainable method to synthesize various unsymmetrical diarylmethyl sulfones, showing good functional group tolerance, scalability, and regioselectivity. Further transformation of the resulting diarylmethyl sulfones provides an efficient route to some functionalized molecules.

Efficient Synthesis of Novel Thioureidobenzamido Alkyl Naphthols in Molten Tetrabutylammonium Bromide

A new series of benzamido alkyl naphthols were synthesized from the multi-component reaction of 4-(3′-methylthioureido)benzamide, aromatic aldehydes and 2-naphthol. Molten tetrabutyl ammonium bromide was used as a very efficient medium for this reaction while the use of common organic solvents gave no or poor yields. This method is an interesting instance of using molten salt as a medium in multicomponent reactions.

Pyramidal Heteroanion-Directed and Reduced MoV-Driven Assembly of Multi-Layered Polyoxometalate Cages

The fabrication of redox-active polyoxometalates (POMs) that can switch between multiple states is critical for their application in electronic devices, yet, a sophisticated synthetic methodology is not well developed for such cluster types. Here we describe the heteroanion-directed and reduction-driven assembly of a series of multi-layered POM cages 1-10 templated by 1-3 redox-active pyramidal heteroanions. The heteroanions greatly affect the selfassembly of the resultant POM cages, leading to the generation of unprecedented three-layered peanut-shaped - 4, 7 and 8 - or bulletshaped - 5 and 6 - structures. The introduction of reduced molybdate is essential for the self-assembly of the compounds and results in mixed-metal (W/Mo), and mixed-valence (WVI/MoV) 1-10, as confirmed by redox titration, UV-Vis-NIR, NMR spectroscopy and mass spectrometry. 11, the tetrabutyl ammonium (TBA) salt derivative of the fully oxidized 3, is produced as a model structure for measurements to confirm that 1-10 are a statistical mixture of isostructural clusters with different ratios of W/Mo. Finally, multilayered POM cages exhibit dipole relaxations due to the presence of mixed valence WVI/MoV metal centers, demonstrating their potential uses for electronic materials.

Pyramidal Heteroanion-Directed and Reduced MoV-Driven Assembly of Multi-Layered Polyoxometalate Cages

The fabrication of redox-active polyoxometalates (POMs) that can switch between multiple states is critical for their application in electronic devices, yet, a sophisticated synthetic methodology is not well developed for such cluster types. Here we describe the heteroanion-directed and reduction-driven assembly of a series of multi-layered POM cages 1-10 templated by 1-3 redox-active pyramidal heteroanions. The heteroanions greatly affect the selfassembly of the resultant POM cages, leading to the generation of unprecedented three-layered peanut-shaped - 4, 7 and 8 - or bulletshaped - 5 and 6 - structures. The introduction of reduced molybdate is essential for the self-assembly of the compounds and results in mixed-metal (W/Mo), and mixed-valence (WVI/MoV) 1-10, as confirmed by redox titration, UV-Vis-NIR, NMR spectroscopy and mass spectrometry. 11, the tetrabutyl ammonium (TBA) salt derivative of the fully oxidized 3, is produced as a model structure for measurements to confirm that 1-10 are a statistical mixture of isostructural clusters with different ratios of W/Mo. Finally, multilayered POM cages exhibit dipole relaxations due to the presence of mixed valence WVI/MoV metal centers, demonstrating their potential uses for electronic materials.