Narrower HOMO-LUMO gap attained by conformational switching through peripheral polyarylation in 1,4,5,8-tetraaza-9,10-anthraquinodimethanes

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A Ruthenium(III)–Oxyl Complex Bearing Strong Radical Character

Proton‐coupled electron‐transfer oxidation of a Ru^II?OH₂ complex, having an N‐heterocyclic carbene ligand, gives a Ru^III?O^. species, which has an electronically equivalent structure of the Ru^IV=O species, in an acidic aqueous solution. The Ru^III?O^. complex was characterized by spectroscopic methods and DFT calculations. The oxidation state of the Ru center was shown to be close to +3; the Ru?O bond showed a lower‐energy Raman scattering at 732 cm^?1 and the Ru?O bond length was estimated to be 1.77(1) Å. The Ru^III?O^. complex exhibits high reactivity in substrate oxidation under catalytic conditions; particularly, benzaldehyde and the derivatives are oxidized to the corresponding benzoic acid through C?H abstraction from the formyl group by the Ru^III?O^. complex bearing a strong radical character as the active species.     

Magnetic tri-axial orientation in (Y1−xErx)2Ba4Cu7O15−y superconductors

We report the tri-axial grain-orientation effects under a modulated rotation magnetic field for (Y_1?xEr_x)₂Ba₄Cu₇O_y [(Y, Er)247]. The magnetic easy axis at room temperature was drastically changed around x ～ 0.1; however, the Er-doping levels for the conversion of magnetic easy axes from the c-axis to the ab-direction and from the a- to b-axes were quite different. Tri-axial single-ion magnetic anisotropy of Er³⁺ was roughly 10 times greater than tri-axial magnetic anisotropy generated by both the superconducting CuO₂ plane and the blocking Cu–O chain layer. An appropriate choice of rare-earth (RE) ions in RE-based cuprate superconductors enables the reduction of the required magnetic field for the production of bulks and thick films based on the magnetic orientation technique.