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 (k(p)) indicates that the symmetry-breaking movement has a crucial role in selectively facilitating k(p) 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.