The demand of sustainable power supply requires high-performance cost-effective energy storage technologies. Here we report a high-rate long-life low-cost sodium-ion battery full-cell system by innovating both the anode and the electrolyte. The redox couple of manganese(I/II) in Prussian blue analogs enables a high-rate and stable anode. Soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering provide direct evidence suggesting the existence of monovalent manganese in the charged anode. There is a strong hybridization between cyano ligands and manganese-3d states, which benefits the electronic property for improving rate performance. Additionally, we employ an organic–aqueous cosolvent electrolyte to solve the long-standing solubility issue of Prussian blue analogs. A full-cell sodium-ion battery with low-cost Prussian blue analogs in both electrodes and co-solvent electrolyte retains 95% of its initial discharge capacity after 1000 cycles at 1C and 95% depth of discharge. The revealed manganese(I/II) redox couple inspires conceptual innovations of batteries based on atypical oxidation states.
Two chiral dimethacrylate and one chiral diacrylate monomer containing an azobenzene group were synthesized and dissolved in a commercial ferroelectric liquid crystal (FLC) host. With two of the monomers, thermally induced radical polymerization with the mixture exposed to linearly polarized irradiation results in a bulk alignment of FLC in the direction perpendicular to the polarization of irradiation light as a result of the photoinduced orientation of azobenzene groups related to the transcis isomerization. The monomer that is most effective for photoalignment of FLC displays a polymer network formed by strings of colloidal particles (∼250 nm in diameter), which exerts a commanding effect on the alignment of FLC as being able to reorient the FLC by changing the polarization direction of subsequent irradiation. The study suggests that the network of colloidal particles is isotropic and that the photoalignment of azobenzene moieties on the large surface of the network dictates the alignment of FLC.
Several divinyl ether and diepoxide monomers bearing an azobenzene moiety were
synthesized and used to investigate the photoalignment of a ferroelectric liquid crystal (FLC) with no
use of surface orientation layers. Azobenzene polymer networks, obtained by cationic polymerization of
the monomers dissolved in the FLC host and exposed to linearly polarized irradiation, were found to be
able to induce and stabilize a bulk alignment of FLC. Photoinduced reorientation of the FLC can also be
achieved by changing the polarization of irradiation light, but in contrast with the use of chiral azobenzene
poly(meth)acrylates, the results suggest a mechanism based on the formation of an anisotropic azobenzene
polyether or polyepoxide network for the commanding effect on the FLC alignment.
The Rh11‐catalyzed carbenoid addition of diazoacetates to olefins was investigated with [Rh2{(4S)‐phox}4] (1;phox = tetrakis[(4S)‐tetrahydro‐4‐phenyloxazol‐2‐one]), [Rh2{(2S)‐mepy}4] (2; mepy = tetrakis[methyl (2S)‐tetrahydro‐5‐oxopyrrole‐2‐carboxylate]), and [Rh2(OAc)4] (3). While catalysis with 2 and 3 afford preferentially trans‐cyclopropanecarboxylates, the cis‐isomers are the major products with 1. In general, the enantioselectivities achieved with 1 and 2 are comparable. Additions catalyzed by 1 are strongly sensitive to steric effects. Highly substituted olefins afford cyclopropanes in only poor yield. The preferential cis‐selectivity observed in reactions catalyzed by 1 is attributed to dominant interactions between the ligand of the catalyst and the substituents of both olefin and diazoacetate, which overrule the steric interactions between olefin and diazoacetate in the transition state for carbene transfer.
Introduction. -We previously reported that dirhodium(I1) catalysts possessing chiral methyl 5-oxopyrrolidine-Zcarboxylate ligands'), [Rh2{(2S)-mepy},] and [Rh2{(2R)-mepy},], are exceptionally effective for highly enantioselective metal carbene transformations [ 1-71. These catalysts were prepared by ligand substitution from dirhodium(I1) acetate, and their design places 2 0 and 2 N donor atoms from the four amide ligands on each octahedral Rh-atom in a cis-configuration. The asymmetric center of the chiral oxopyrrolidinecarboxylate ligand is the sp3-hybridized C-atom bonded to the N donor
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