Symmetry‐Breaking Triplet Excited State Enhances Red Afterglow Enabling Ubiquitous Afterglow Readout

Abstract

Abstract Molecular vibrations are often factors that deactivate luminescence. However, if there are molecular motion elements that enhance luminescence, it may be possible to utilize molecular movement as a design guideline to enhance luminescence. Here, the authors report a large contribution of symmetry‐breaking molecular motion that enhances red persistent room‐temperature phosphorescence (RTP) in donor‐π‐donor conjugated chromophores. The deuterated form of the donor‐π‐donor chromophore exhibits efficient red persistent RTP with a yield of 21% and a lifetime of 1.6 s. A dynamic calculation of the phosphorescence rate constant (kp) indicates that the symmetry‐breaking movement has a crucial role in selectively facilitating kp without increasing nonradiative transition from the lowest triplet excited state. Molecules exhibiting efficient red persistent RTP enable long‐wavelength excitation, indicating the suitability of observing afterglow readout in a bright indoor environment with a white‐light‐emitting diode flashlight, greatly expanding the range of anti‐counterfeiting applications that use afterglow.

Keywords

• molecular distortion
• persistent room temperature phosphorescence
• red phosphorescence
• symmetry‐breaking
• symmetry‐forbidden transition