Synthesis, Characterization, and Reactivity of a Hypervalent-Iodine-Based Nitrooxylating Reagent.

Herein, the synthesis and characterization of a hypervalent-iodine-based reagent that enables a direct and selective nitrooxylation of enolizable C-H bonds to access a broad array of organic nitrate esters is reported. This compound is bench stable, easy-to-handle, and delivers the nitrooxy (-ONO2 ) group under mild reaction conditions. Activation of the reagent by Brønsted and Lewis acids was demonstrated in the synthesis of nitrooxylated ß-keto esters, 1,3-diketones, and malonates, while its activity under photoredox catalysis was shown in the synthesis of nitrooxylated oxindoles. Detailed mechanistic studies including pulse radiolysis, Stern-Volmer quenching studies, and UV/Vis spectroelectrochemistry reveal a unique single-electron-transfer (SET)-induced concerted mechanistic pathway not reliant upon generation of the nitrate radical.

Circularly polarized luminescence from Tb(III) interacting with chiral polyether macrocycles.

A straightforward two-step synthesis protocol affords a series of chiral amide-based bis-pyridine substituted polyether macrocycles. One ligand is particularly able to complex terbium(III) ions spontaneously. Upon complexation, interesting chiroptical properties are observed both in absorbance (ECD) and in fluorescence (CPL). In ligand-centered electronic circular dichroism, a sign inversion coupled with a signal enhancement is measured; while an easily detectable metal-centered circularly polarized luminescence with a glum of 0.05 is obtained for the main 5D4 → 7F5 terbium transition. The coordination mode and structure of the complex was studied using different analysis methods (NMR analysis, spectrophotometric titration and solid-state elucidation).