Phosphinine Selenide: Noncovalent Interactions with Organoiodines and Elemental Iodine, and Reactivity towards Potassium Cyanide.

Invited for this month's cover is the group of Prof. Dr. Christian Müller from Freie Universität Berlin, Germany.

Photochemically deoxygenating gels for triplet-triplet annihilation photon-upconversion performed under air.

For an efficient triplet-triplet annihilation photon upconversion (TTA-UC) process, matrices in which sensitizers and emitters are dispersed should not only allow molecular diffusions but also protect triplet excited states from oxygen-quenching. In this work, two photochemically deoxygenating gels, a poly(-vinyl-2-pyrrolidone) (PVP) gel and a limonene gel, were prepared for TTA-UC performed under air. These two gels are optically transparent in the visible region and can serve as a scavenger for sensitized singlet oxygen.

Phospholenes from Phosphabenzenes by Selective Ring Contraction.

A 3-amino-functionalized phosphabenzene (phosphinine) has been synthesized and structurally characterized. The pyramidalized nitrogen atom of the dimethylamino substituent indicates only a weak interaction between the lone pair of the nitrogen atom and the aromatic phosphorus heterocycle, resulting in somewhat basic character. It turned out that the amino group can indeed be protonated by HCl.

Phosphinine Selenide: Noncovalent Interactions with Organoiodines and Elemental Iodine, and Reactivity towards Potassium Cyanide.

A co-crystalline adduct consisting of a phosphinine selenide and an organohalide was obtained by slow evaporation of the solvent from a mixture of 2,6-bis(trimethylsilyl)phosphinine selenide and 1,4-diiodotetrafluorobenzene (1,4-TFDIB). The crystallographic characterization of the product shows π-π stacking, F⋅⋅⋅H hydrogen bonding between 1,4-TFDIB and the phosphinine selenide, as well as F⋅⋅⋅F interactions between 1,4-TFDIB molecules. Moreover, the phosphorus heterocycle could be crystallized with diiodine to form a 1 : 1 adduct.

Borane Adducts of Aromatic Phosphorus Heterocycles: Synthesis, Crystallographic Characterization and Reactivity of a Phosphinine-B(C F ) Lewis Pair.

A phosphinine-borane adduct of a Me Si-functionalized phosphinine and the Lewis acid B(C F ) has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α-position of the phosphorus heterocycle. In contrast, the reaction of B H with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine-borane adducts that is determined by the Lewis basicity of the phosphinine.

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide.

The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of J =883 Hz is in line with a P-Se bond of high s-character. The σ-electron donating Me Si-substituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C H P, as confirmed by the calculated gas phase basicities.

A Prototype of a Volumetric Three-Dimensional Display Based on Programmable Photo-Activated Phosphorescence.

A proof-of-principle prototype of a volumetric 3D-displaying system is demonstrated by utilizing the photo-activated phosphorescence of two long-lived phosphorescent metal-porphyrins in dimethyl sulfoxide (DMSO), a photochemically deoxygenating solvent. The first phosphorescent sensitizer, Pt(TPBP), absorbs a light beam with a wavelength of 635 nm, and the sensitized singlet oxygen is scavenged by DMSO. The second phosphorescent emitter, Pt(OEP), absorbs a light beam with a wavelength of 532 nm and visibly phosphoresces only in the deoxygenated zone generated by the first sensitizer.

Photo-writing self-erasable phosphorescent images using poly(N-vinyl-2-pyrrolidone) as a photochemically deoxygenating matrix.

A passive photo-writing approach for optical data recording is described. Poly(N-vinyl-2-pyrrolidone) has been demonstrated as a photochemically deoxygenating polymeric matrix in which phosphorescent images from a molecular phosphor could be written by photo-activation and be competitively erased by diffusional oxygen quenching.

Photochemically deoxygenating solvents for triplet-triplet annihilation photon upconversion operating in air.

Sulfoxides and cyclic ureas are photochemically deoxygenating solvents in which the oxidative stress could be released and efficient triplet-triplet annihilation photon upconversion (TTA-UC) can operate in air. Such solvents can be practically screened out by harnessing the property of photo-activated phosphorescence.

Combined inhibition of EGFR and c-ABL suppresses the growth of fulvestrant-resistant breast cancer cells through miR-375-autophagy axis.

Fulvestrant is the FDA-approved "pure anti-estrogen" agent for malignant breast cancer therapy. But endocrine resistance causes drug failure. A new approach is desired for fulvestrant-resistant breast cancer (FRBC) therapy.