Two-Step Oxidation Synthesis of Sulfur with a Red Aggregation-Induced Emission

Angew Chem Int Ed Engl. 2020 Jun 15;59(25):9997-10002. doi: 10.1002/anie.201915511. Epub 2020 Jan 29.

Abstract

Sulfur is not normally considered a light-emitting material, even though there have been reports of a dim luminescence of this compound in the blue-to-green spectral region. Now, it is shown how to make red-emissive sulfur by a two-step oxidation approach using elemental sulfur and Na2 S as starting materials, with a high photoluminescence quantum yield of 7.2 %. Polysulfide is formed first and is partially transformed into Na2 S2 O3 in the first step, and then turns back to elemental S in the second step. The elevated temperature and relatively oxygen-deficient environment during the second step transforms Na2 S2 O3 into Na2 SO3 incorporated with oxygen vacancies, thus resulting in the formation of a solid-state powder consisting of elemental S embedded in Na2 SO3 . It shows aggregation-induced emission properties, attributed to the influence of oxygen vacancies on the emission dynamics of sulfur by providing additional lower energy states that facilitate the radiative relaxation of excitons.

Keywords: aggregation-induced emission; elemental sulfur; oxidation; oxygen vacancies; phosphorescence.