2-Phenylimidazoline based porous hypercrosslinked ionic polymers afforded high yields in the cycloaddition of epoxides with ambient or diluted CO2 (0.15 bar CO2 and 0.85 bar N2) under low or room temperature.

Activation of aryl chlorides for Suzuki−Miyaura coupling (SMC) reactions is particularly challenging for heterogeneous catalysts due to the chemically inert nature of the C−Cl bond. Herein, the multifunctional Pd/Au/ porous nanorods of CeO 2 (PN-CeO 2 ) catalysts with a well-defined spatial configuration deliver the first example of heterogeneous catalysts to activate the strong C−Cl bond under the irradiation of visible light (>400 nm) at room temperature. PN-CeO 2 with strong basicity not only provides the photogenerated electrons to enrich the electron density of metal nanoparticles but also generates holes for activation of arylboronic acids. Meanwhile, due to the strong local surface plasma resonance, the hot electrons from Au nanoparticles excited by visible light can be injected into Pd nanocatalysts that are spatially contacted with Au nanoparticles. Thus, Pd nanocatalysts with significantly enriched electron density efficiently activate the aryl chlorides under the visible light irradiation at room temperature. The high catalytic activity and reusability of multifunctional photocatalysts associated with full use of the photogenerated electrons and holes inspire the future exploitation for the activation of unreactive chemical bonds under mild conditions.

Herein, we report a highly regio- and enantioselective copper-catalyzed reductive hydroxymethylation of styrenes and 1,3-dienes with 1 atm of CO. Diverse important chiral homobenzylic alcohols were readily prepared from styrenes. Moreover, a variety of 1,3-dienes also were converted to chiral homoallylic alcohols with high yields and excellent regio-, enantio-, and Z/E-selectivities. The utility of this transformation was demonstrated by a broad range of styrenes and 1,3-dienes, facile product modification, and synthesis of bioactive compounds (R)-(-)-curcumene and (S)-(+)-ibuprofen. Mechanistic studies demonstrated the carboxylation of phenylethylcopper complexes with CO as one key step.

Reported herein is a novel visible-light photoredox system with Pd(PPh ) as the sole catalyst for the realization of the first direct cross-coupling of C(sp )-H bonds in N-aryl tetrahydroisoquinolines with unactivated alkyl bromides. Moreover, intra- and intermolecular alkylations of heteroarenes were also developed under mild reaction conditions. A variety of tertiary, secondary, and primary alkyl bromides undergo reaction to generate C(sp )-C(sp ) and C(sp )-C(sp ) bonds in moderate to excellent yields. These redox-neutral reactions feature broad substrate scope (>60 examples), good functional-group tolerance, and facile generation of quaternary centers. Mechanistic studies indicate that the simple palladium complex acts as the visible-light photocatalyst and radicals are involved in the process.

The first catalytic hydrocarboxylation of enamides and imines with CO to generate valuable α,α-disubstituted α-amino acids is reported. Notably, excellent chemo- and regio-selectivity are achieved, significantly different from previous reports on β-carboxylation of enamides, homocoupling or reduction of imines. Moreover, this transition-metal-free procedure exhibits low loading of an inexpensive catalyst, easily available substrates, mild reaction conditions, high efficiency, facile scalability and easy product derivatization, providing great potential for application in organic synthesis, pharmaceutical chemistry, and biochemistry.

An effective Cu-catalyzed selective formal carboxylation of C–F bonds with an atmospheric pressure of CO2 is reported. A variety of gem-difluoroalkenes, gem-difluorodienes, and α-trifluoro-methyl alkenes show high reactivity and selectivity for this ipso monocarboxylation. Under mild conditions, diverse important α-fluoroacrylic acids and α,α-difluorocarboxylates are obtained in good-to-high yields. Moreover, this operationally simple protocol features good functional group tolerance, is readily scalable, and the resulting products are readily converted into bioactive α-fluorinated carbonyl compounds, indicating potential application in biochemistry and drug discovery. Mechanistic studies reveal that fluorinated boronate esters might be vital intermediates in this transformation.

Controlled-porosity Si thin films suitable for use as high-aspect-ratio microbattery electrodes were produced using the glancing angle deposition ͑GLAD͒ technique. GLAD is a high-vacuum physical vapor deposition method that can be used to produce a variety of film morphologies from most vacuum-compatible materials. No lithographic steps were required to create the porous, columnar thin films. Initial electrochemical results indicate large gravimetric and areal capacities ͑3600 mAh/g, 90 Ah/cm 2 , respectively͒, and good capacity retention ͑3000 mAh/g after 70 charge/discharge cycles͒ can be obtained from Si vertical post morphology films. Areal capacity and capacity retention can likely be further improved by optimizing the film morphology, electrode material composition, and cycling conditions.

The quantum tunnelling of magnetization was observed in [Zn2Dy2], contrarily it was quenched in [Mn2Dy2] and [Co2Dy2] by spin–spin exchange.