Intramolecular Triplet–Triplet Annihilation Photon Upconversion in Diffusionally Restricted Anthracene Polymer

[Image: see text] In the strive to develop triplet–triplet annihilation photon upconversion (TTA-UC) to become applicable in a viable technology, there is a need to develop upconversion systems that can function well in solid states. One method to achieve efficient solid-state TTA-UC systems is to replace the intermolecular energy-transfer steps with the corresponding intramolecular transfers, thereby minimizing loss channels involved in chromophore diffusion. Herein, we present a study of photon upconversion by TTA internally within a polymeric annihilator network (iTTA). By the design of the annihilator polymer and the choice of experiment conditions, we isolate upconversion emission governed by iTTA within the annihilator particles and eliminate possible external TTA between separate annihilator particles (xTTA). This approach leads to mechanistic insights into the process of iTTA and makes it possible to explore the upconversion kinetics and performance of a polymeric annihilator. In comparison to a monomeric upconversion system that only functions using xTTA, we show that upconversion in a polymeric annihilator is efficient also at extremely low annihilator concentrations and that the overall kinetics is significantly faster. The presented results show that intramolecular photon upconversion is a versatile concept for the development of highly efficient solid-state photon upconversion materials.