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A new family of boron(III) chelates is introduced whereby molecular chirality, confirmed by circular dichroism, is imported during synthesis such that isolation of the diastereoisomers does not require separation procedures. The photophysical properties of two members of the family have been examined: the N,O,O‐salicylaldehyde‐based derivative shows pronounced intramolecular charge‐transfer character in fluid solution and is weakly fluorescent, with a large Stokes shift. The corresponding 2‐methylamino‐benzaldehyde‐derived N,N,O‐chelate absorbs and fluoresces in the visible region with a much smaller Stokes shift. Orange fluorescence is also observed for this compound as a cast film. Temperature‐dependence studies show that decay of the fluorescent state is weakly activated but emission is less than quantitative at 77 K. Quite rare for boron(III)‐based chelates, this derivative undergoes intersystem crossing to form a meta‐stable triplet‐excited state. X‐ray crystal structures are reported for both compounds, along with simulated ECD spectra.

Long-range electrostatic interactions are sufficient to cause sequential ionization of the terminal groups in a BOPHY-based supermolecule.