Oxidation of an Internal-Edge-Substituted [5]Helicene-Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence.

Invited for the cover of this issue are the groups of Kazuteru Usui and Satoru Karasawa at Showa Pharmaceutical University, and Yoshitane Imai at Kindai University. The image depicts how a phosphine-oxide-bearing helicene exhibits markedly enhanced CPL response in the excited state compared with that of one with a corresponding phosphine. Read the full text of the article at 10.1002/chem.202202922.

Oxidation of an Internal-Edge-Substituted [5]Helicene-Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence.

Small chiral organic molecules with CD properties are in high demanded due to their potential use in promising electronic and biological applications. Herein, we reveal a system in which the oxidation of a phosphino group to the corresponding phosphine oxide on the inner rim of a helicene derivative induces a CPL response. Laterally π-extended 7,8-dihydro[5]helicenes bearing phosphine and phosphine oxide groups on their inner helical rims (i. e., the C1 position) were synthesized, and their helical structures were unambiguously determined by X-ray crystallography. The photophysical (UV/visible and emission) and chiroptical properties of these compounds were investigated in various solvents. Despite their structural similarities, phosphine oxide showed a significantly better CPL response than phosphine, with a high dissymmetry factor for emission (|glum |=(1.3-1.9)×10-3 ) that can be attributed to structural changes in the interior of the helicene helix.

ß-Glycosyl Trifluoroborates as Precursors for Direct α-C-Glycosylation: Synthesis of 2-Deoxy-α-C-glycosides.

C-Glycosides are metabolically stable mimics of natural O-glycosides and are expected to be useful tools for investigation of the biological functions of glycans. Here, we describe the synthesis of a series of aryl and vinyl C-glycosides by stereoinvertive sp3-sp2 cross-coupling reactions of 2-deoxyglycosyl boronic acid derivatives with aryl or vinyl halide, mediated by a photoredox/nickel dual catalytic system. Hydrogenation of the vinyl C-glycosides afforded C-linked 2'-deoxydisaccharide analogues.

Movable high-Q nanoresonators realized by semiconductor nanowires on a Si photonic crystal platform.

Subwavelength semiconductor nanowires have recently attracted interest for photonic applications because they possess various unique optical properties and offer great potential for miniaturizing devices. However, realizing tight light confinement or efficient coupling with photonic circuits is not straightforward and remains a challenge. Here we show that a high-Q nanocavity can be created by placing a single III­V semiconductor nanowire with a diameter of under 100 nm in a grooved waveguide in a Si photonic crystal, by means of nanoprobe manipulation. We observe very fast spontaneous emission (91 ps) from nanowires accelerated by the strong Purcell enhancement in nanocavities, which proves that very strong light confinement can be achieved. Furthermore, this system enables us to move the nanocavity anywhere along the waveguide. This configuration provides a significant degree of flexibility in integrated photonics and permits the addition and displacement of various functionalities of III­V nanocavity devices in Si photonic circuits.

Ultrahigh-Q nanocavities written with a nanoprobe.

High-Q nanocavities have been extensively studied recently because they are considered key elements in low-power photonic devices and integrated circuits. Here we demonstrate that ultrahigh-Q (>10(6)) nanocavities can be created by employing scanning probe lithography on a prepatterned line defect in a silicon photonic crystal. This is the first realization of ultrahigh-Q nanocavities by the postprocess modification of photonic crystals. With this method, we can form an ultrahigh-Q nanocavity with controllable cavity parameters at an arbitrary position along a line defect. Furthermore, the fabricated nanocavity achieves ultralow power all-optical bistable operation owing to its large cavity enhancement effect. This demonstration indicates the possibility of realizing photonic integrated circuits on demand, where various circuit patterns are written with a nanoprobe on a universal photonic crystal substrate.

Vibrational spectra and chemical quantum calculations for 2-adamantylamino-5-nitropyridine crystals--a novel material for laser Raman converters.

Polycrystalline infrared and polarized FT-Raman spectra have been measured for 2-adamantylamino-5-nitropyridine, a novel organic material for laser Raman converters. The assignment of IR and Raman bands is given on the basis of DFT calculations. The spectroscopic studies have not indicated the presence of any significant intermolecular interactions in the crystal structure of this compound. The lines observed in the stimulated Raman spectrum of this crystal are assigned to the respective molecular vibrations.