Reversible Self-Assembling of Boryl Radical Anions to Their Diradicals with Tunable Singlet Ground States

Chemistry. 2019 Mar 15;25(16):4031-4035. doi: 10.1002/chem.201804918. Epub 2018 Dec 14.

Abstract

Two novel boron-centered diradicals based on dimesitylpyridine borane (1) were synthesized by the self-assembling of the corresponding radical sodium and potassium salts, respectively. The sodium diradical was obtained by re-dissolving the crystals of the radical salt 1Na in toluene, while the potassium diradical was directly obtained by the reduction of 1 with potassium in THF. The diradicals could be converted back to their radical anions in THF solution, forming a reversible process. EPR spectroscopy and SQUID measurements, together with theoretical calculations, show that the diradicals have singlet ground states with excited triplet states. Their singlet-triplet energy gaps are tunable with metals.

Keywords: EPR spectroscopy; SQUID measurements; boron; boron-based diradicals; diradicals; self-assembly.