A series of perylene derivatives are prepared as triplet energy acceptors for triplet-triplet annihilation (TTA) assisted upconversion. The aim is to optimize the energy levels of the T1 and S1 states of the triplet acceptors, so that the prerequisite for TTA (2E(T1) > E(S1)) can be better satisfied, and eventually to increase the upconversion efficiency. Tuning of the energy levels of the excited states of the triplet acceptors is realized either by attaching aryl groups to perylene (via single or triple carbon-carbon bonds), or by assembling a perylene-BODIPY dyad, in which the components present complementary S1 and T1 state energy levels. The S1 state energy levels of the perylene derivatives are generally decreased compared to perylene. The anti-Stokes shift, TTA, and upconversion efficiencies of the new triplet acceptors are improved with respect to the perylene hallmark. For the perylene-BODIPY dyads, the fluorescence emission was substantially quenched in polar solvents. Moreover, we found that extension of the π-conjugation of BODIPY energy donor significantly reduces the energy level of the S1 state. Low S1 state energy level and high T1 state energy level are beneficial for triplet photosensitizers.

"Chemistry-on-the-complex" synthetic methods have allowed the selective addition of 1-ethynylpyrene appendages to the 3-, 5-, 3,8- and 5,6-positions of Ir -coordinated 1,10-phenanthroline via Sonogashira cross-coupling. The resulting suite of complexes has given rise to the first rationalization of their absorption and emission properties as a function of the number and position of the pyrene moieties. Strong absorption in the visible region (e.g. 3,8-substituted Ir-3: λ =481 nm, ϵ=52 400 m cm ) and long-lived triplet excited states (e.g. 5-substituted Ir-2: τ =367.7 μs) were observed for the complexes in deaerated CH Cl . On testing the series as triplet sensitizers for triplet-triplet annihilation upconversion, those Ir complexes bearing pyrenyl appendages at the 3- and 3,8-positions (Ir-1, Ir-3) were found to give optimal upconversion quantum yields (30.2 % and 31.6 % respectively).

A long-lived dual phosphorescence triplet photosensitiser: for TTA upconversion and PDT.