Asymmetric Core-Expanded BOPYOs: Facile Synthesis and Optical Properties.

N,O-bidentate BF2 complexes with five- and six-membered core rings have been thoroughly investigated. However, the development of seven-membered N,O-boron complexes is still an area to be explored. We have developed BF3 ⋅ OEt2 -induced self-condensation and coordination reactions based on a single starting material, which had been elucidated by experiment and calculation. This parent asymmetric core-expanded borondifluoride-(Z)-1,3-di(1H-pyrrol-2-yl)but-2-en-1-one (BOPYO) showed reactivity with a wide range of aldehydes, thus providing a series of conjugation BOPYOs. Moreover, a BOPYO derivative with a dimethylamino group was developed as a new NIR dye that responds to acid with favorable photophysical properties based on intramolecular charge transfer effect.

Loading Phlorins with Fullerenes by a [4 + 2]-Cycloaddition Reaction: Regulation of the Regioselectivity by Pyrrole Linkage Modes.

Sulfolenopyrrole-based normal and N-confused phlorins have been constructed to address the seldom touched phlorin functionalization and simultaneously explore the effect of the pyrrole linkage modes (αα, αß) on the [4 + 2] cycloaddition reaction. The common sulfolenophlorin 1 contains two sulfolenopyrroles with the same reactivity upon tautomerization and undergoes stepwise [4 + 2]-cycloaddition with fullerene to furnish monoadduct 1-C60 and bisadduct 1-2C60 with a total yield up to 76%. By contrast, the presence of the confused pyrrole in 2 fixes the π-system owing to the low tendency to tautomerize and enables the two sulfolenopyrroles to exhibit in different fashions (i.e., normal NH-type and imino-type). Notably, under milder conditions (120 °C), the monofullerenoadduct 2-C60 forms rapidly and has been isolated from the [4 + 2] cycloaddition reaction of 2 and fullerene as the predominant fraction, accompanied by a trace amount of bisadduct 2-2C60. Raising the temperature to 140 °C did not improve the yield of 2-2C60. The structural analysis of 2-C60 indicates the attachment of fullerene at the iminopyrrole part. The high regioselectivity in the [4 + 2] cycloaddition of the imino-type sulfolenopyrrole unit has been rationalized thermodynamically by the DFT calculation on the relative energy of the two diene intermediates.

Aerobic Oil-Phase Cyclic Magnetic Adsorption to Synthesize 1D Fe2O3@TiO2 Nanotube Composites for Enhanced Visible-Light Photocatalytic Degradation.

In this work, Fe2O3@TiO2 nanostructures with staggered band alignment were newly designed by an aerobic oil-phase cyclic magnetic adsorption method. XRD and TEM analyses were performed to verify the uniform deposition of Fe2O3 nanoparticles on the nanotube inner walls of TiO2. The steady-state degradation experiments exhibited that 1FeTi possessed the most superior performance, which might be ascribable to the satisfying dark adsorption capacity, efficient photocatalytic activity, ease of magnetic separation, and economic efficiency. These results indicated that the deposition of Fe2O3 into TiO2 nanotubes significantly enhanced the activity of Fe2O3, which was mainly ascribed to the Fe2O3-induced formation of staggered iron oxides@TiO2 band alignment and thus efficient separation of h+ and e-. Furthermore, the PL intensity and lifetime of the decay curve were considered as key criterions for the activity's evaluation. Finally, the leaching tests and regeneration experiments were also performed, which illustrated the inhibited photodissolution compared with TiO2/Fe3O4 and stable cycling ability, enabling 1FeTi to be a promising magnetic material for photocatalytic water remediation.