Dianionic and Neutral Diboron-Centered Classical Diradicaloids.

Herein, we report the syntheses and electronic structures of crystalline dianionic as well as neutral diboron-centered classical diradicaloids as boron analogues of classical Thiele, Chichibabin, and Müller (this only for dianionic diradicaloids!) hydrocarbons. These are based on borane radical anion and NHC-stabilized boryl radical spin carriers, respectively. All these dianionic diboron-centered diradicaloids exhibit triplet population at room temperature regardless of the π-conjugated spacer: p -phenylene, p , p' -biphenylene, or p , p″ -terphenylene. In the case of neutral diboron-centered diradicaloids, the employed π-conjugated spacer plays a crucial role for the triplet population at room temperature: EPR inactive for p -phenylene vs EPR active for p , p' -biphenylene. The findings emphasize the importance of the spin carriers for the resulting ground-state: borane radical anion vs NHC-stabilized boryl radical along with the pivotal role of the π-conjugated spacer as spin-coupler between two spins. Notably, 100 years (a century) after the first report by Krause of the triphenyl borane radical-anion, being isoelectronic to the triphenylmethyl radical, we convey borane radical anion-based diradicaloids. Furthermore, while donor-stabilized boryl radicals were introduced in the 1980s by Giles and Roberts, said concept is herewith being extended to NHC-stabilized boryl radical-based diradicaloids.