Capturing Doublet Intermediate Emitters by Chemically Crosslinking Confinement towards Spatiotemporal Encryption.

Photoluminescence is one of the most meticulous ways to manipulate light energy. Typical photoluminescent emitters are mostly stable substances with a pure photophysical process of spontaneous photon-emission from their excited states. Intermediate emitters are elusive attributing to their synchronous energy transfer process including photophysical and incomplete photochemical pathways. An intermediate emitter containing radicals is more difficult to be observed due to its inherent chemical reactivity. Here, these challenges are overcome by spontaneously formed space limitations in polymer crosslinking networks meanwhile chemically active intermediates are captured. These doublet intermediates exhibit unique long-wavelength emissions under chemically crosslinking confinement conditions, and their luminous mechanism provides a novel perspective for designing intermediate emitters with liquid-crystal character and photoresponsive features towards spatiotemporal encryption, promising for the detection of photochemical reactions and the development of fascinating luminescent systems.