Multiple-State Emissions from Neat, Single-Component Molecular Solids: Suppression of Kasha's Rule

Three rigid and structurally simple heterocyclic stilbene derivatives, (E)-3H,3'H-[1,1'-biisobenzofuranylidene]-3,3'-dione, (E)-3-(3-oxobenzo[c] thiophen-1(3H)-ylidene)isobenzofuran-1(3H)-one, and (E)-3H,3'H-[1,1'-bibenzo[c] thiophenylidene]-3,3'-dione, are found to fluoresce in their neat solid phases, from upper (S₂ ) and lowest (S₁ ) singlet excited states, even at room temperature in air. Photophysical studies, single-crystal structures, and theoretical calculations indicate that large energy gaps between S₂ and S₁ states (T₂ and T₁ states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S₂ excited states (phosphorescence from T₂ excited states). These results, including unprecedented fluorescence quantum yields (2.3-9.6 %) from the S₂ states in the neat solids, establish a unique molecular skeleton for achieving multi-colored emissions from upper excited states by "suppressing" Kasha's rule.