Exploiting the benefit of S₀ → T₁ excitation in triplet–triplet annihilation upconversion to attain large anti-stokes shifts: tuning the triplet state lifetime of a tris(2,2′-bipyridine) osmium(<scp>ii</scp>) complex

Abstract

Os(ii) complexes are particularly interesting for triplet-triplet annihilation (TTA) upconversion, due to the strong direct S₀→ T₁ photoexcitation, as in this way, energy loss is minimized and large anti-Stokes shift can be achieved for TTA upconversion. However, Os(bpy)₃ has an intrinsic short T₁ state lifetime (56 ns), which is detrimental for the intermolecular triplet-triplet energy transfer (TTET), one of the crucial steps in TTA upconversion. In order to prolong the triplet state lifetime, we prepared an Os(ii) tris(bpy) complex with a Bodipy moiety attached, so that an extended T₁ state lifetime is achieved by excited state electronic configuration mixing or triplet state equilibrium between the coordination center-localized state (³MLCT state) and Bodipy ligand-localized state (³IL state). With steady-state and time-resolved transient absorption/emission spectroscopy, we proved that the ³MLCT is slightly above the ³IL state (by 0.05 eV), and the triplet state lifetime was prolonged by 31-fold (from 56 ns to 1.73 μs). The TTA upconversion quantum yield was increased by 4-fold as compared to that of the unsubstituted Os(ii) complex.