Photochromic System among Boron Hydrides: The Hawthorne Rearrangement

Photoswitchable molecules have attracted wide interest for many applications in chemistry, physics, and materials science. In this work, we revisit the reversible photochemical and thermal rearrangements of the two B₂₀H₁₈^2- isomers reported by Hawthorne and Pilling in 1966, whose mechanism had not been understood so far. We investigate the rearrangements by means of a joint experimental and computational study with the outcome that B₂₀H₁₈^2- represents the first boron-based photochromic system ever reported. Both photochemical and thermal isomerizations occur through the same intermediate and involve a diamond-square-diamond (DSD) mechanism. Given the absence within boron chemistry of named chemical reactions as opposed to organic chemistry, we propose to label the B₂₀H₁₈^2- photo- and thermal isomerization processes as the Hawthorne rearrangement.