Single-Molecule-based White-Light Emissive Organic Solids with Molecular-Packing-Dependent Thermally Activated Delayed Fluorescence.

White-light-emitting single molecules have attracted broad attention because of their great potential for use in flat-panel displays and future light sources. We report a unique molecule of 3-(diphenylamino)-9H-xanthen-9-one (3-DPH-XO), which was found to exhibit bright white-light emission in the solid state caused by the spontaneous formation of a mixture with different polymorphs. Single-crystal analyses demonstrate that noncovalent interactions (such as π···π stacking, hydrogen bonding, and C-H···π interactions) induce different stacking arrangements (polymorphs A, B, and C) with different photophysical properties in a molecular solid. In addition, crystals B and C with the acceptor···acceptor stacking feature show the thermally activated delayed fluorescence (TADF) characteristics, indicating that appropriate noncovalent interactions could enhance the reverse intersystem crossing process and consequently lead to delayed fluorescence. This discovery provides an effective strategy for the design of new white-light-emitting single molecules as well as TADF materials.