Divergent and Multi-Stage Photoisomerization of Four-Coordinated Boron Compounds with a Naphthyl-Pyridyl/Thiazolyl Backbone

Examination of the photoreactivity of a new class of N,C-chelate organoboron compounds, including a series of unsymmetrically substituted boron molecules, B(naph-pyridyl)(Ar¹)(Ar²) and B(naph-thiazolyl)(Ar¹)(Ar²), led to the discovery of new and divergent photothermal isomerization phenomena. These include the clean and regioselective photoisomerization by unsymmetrical boron, forming borepin isomers, some of which further isomerize to the corresponding boratanorcaradiene diastereomer pairs as a result of the generation of two chiral centers. Significantly, the boratanorcaradienes involving a 3-thienyl substituent on boron were found to thermally convert to BN-fluoranthene annulated borapentalene via an unprecedented reversible boratacyclopropane–boratacyclopentene rearrangement. Changing the pyridyl donor to a thiazolyl donor on the boron was found to provide the B(naph-thiazolyl)(Mes)₂ compounds with a distinct new photoisomerization pathway—instead of borepin, forming new blue fluorescent polycyclic azaborinine species. This work illustrates the richness and complexity of boron photochemistry.