Highly Fluorescent Bipyrrole-Based Tetra-BF₂ Flag-Hinge Chromophores: Achieving Multicolor and Circularly Polarized...

This study reports the facile syntheses of tetra-boron difluoride (tetra-BF₂ ) complexes, flag-hinge-like molecules that exhibit intense green-to-orange luminescence in solution and yellow-to-red emission in the solid states. Single-crystal structure analysis and density functional theory calculations suggested a bent structure of this series of compounds. The complexes also exhibited excellent optical properties, with quantum yields reaching 100 % and a large Stokes shift. These properties were attributed to the altered bending angle of the molecule in the S₁ excited state. As the rotational motion was suppressed around the 2,2'-bipyrrole axis, atropisomers with axial chirality were formed, which are optically resolvable into (R) and (S)-enantiomers through a chiral column. The atropisomers thus function as circularly polarized luminescent (CPL) materials, in which the color (green, green-yellow, and yellow) can be varied by controlling the aggregation state. This rational design of multi-BF₂ complexes can potentially realize novel photofunctional materials.