Representative types of boron-based molecular systems that respond to external stimuli such as temperature, pressure, light, or chemicals (oxygen, acid, base etc.) are described in this review article. The boron molecules are classified according to their operating mechanisms, with emphasis on systems, which are based on switchable boron-donor bonds and switchable excited states.
Asymmetric N,C-chelate organoboron compounds bearing two different aryl groups at the boron center undergo photoisomerization reactions that involve exclusively the less bulky aryl group, generating various strongly colored "dark isomers". These species thermally isomerize to 4bH-azaborepin molecules by direct hydrogen atom transfer from a borirane cycle to the pyridyl moiety and ring expansion. Mechanistic insight into these highly regioselective transformations was obtained from kinetic data and through computational studies.
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