Formation of a P₁₆^2– Ink from Elemental Red Phosphorus in a Thiol–Amine Mixture

Abstract

A P 16 2− polyphosphide dianion ink was produced by the reaction of red phosphorus with a binary thiol−amine mixture of ethanethiol (ET) and ethylenediamine (en). The polyphosphide was identified by solution 31 P NMR spectroscopy and electrospray ionization mass spectrometry. This solute was compared to the reaction products of white phosphorus (P 4 ) and other elemental pnictides in the same solvent system. The reaction of P 4 with ET and en gives the same P 16 2− polyphosphide; however, the easier handling and lower reactivity of red phosphorus highlights the novelty of that reaction. Elemental arsenic and antimony both give mononuclear pnictogen−sulfide−thiolate complexes upon reaction with ET and en under otherwise identical conditions, with this difference likely resulting from the greater covalency and tendency of phosphorus to form P−P bonds.

A Route to High Thermoelectric Performance: Solution‐Based Control of Microstructure and Composition in Ag2Se

“…in the isotope pattern of polyphosphides in en:EtSH mixtures, where the evennumbered polyphosphides appeared protonated. [40] Mixing the two solutions at RT immediately results in the precipitation of polycrystalline Ag 2 Se, indicating that the reaction between the silver thiolate complexes and the polyselenides is energetically favorable. Analysis of the supernatant shows a peak corresponding to [Ag 5 (EtS) 6 Se] − in ESI-MS (Figure S2, Supporting Information), indicating that silver polyselenides could be intermediates in the formation of crystalline Ag 2 Se in saturated conditions.…”

“…in the isotope pattern of polyphosphides in en:EtSH mixtures, where the even‐numbered polyphosphides appeared protonated. [ 40 ]…”