Triplet energy transfer enables efficient Z-to-E photoswitching of azobenzenes even with near-infrared light. Ultrafast intersystem crossing of azobenzene makes the process entropy-driven and enables the use of endothermic sensitizer-azobenzene pairs.

Expanding the anti-Stokes shift for triplet−triplet annihilation upconversion (TTA-UC) systems with high quantum yields without compromising power density thresholds (I th ) remains a critical challenge in photonics. Our studies reveal that such expansion is possible by using a highly endothermic TTA-UC pair with an enthalpy difference of +80 meV even in a polymer matrix 1000 times more viscous than toluene. Carrying out efficient endothermic triplet−triplet energy transfer (TET) requires suppression of the reverse annihilator-to-sensitizer TET, which was achieved by using sensitizers with high molar extinction coefficients and long triplet state lifetimes as well as optimized annihilator concentrations. Under these conditions, the sensitizer-toannihilator forward TET becomes effectively entropy driven, yielding upconversion quantum yields comparable to those achieved with the exothermic TTA-UC pair but with larger anti-Stokes shifts and even lower I th , a previously unattained achievement.

Triplet–triplet annihilation upconversion (TTAUC) is a power density-dependent process where photons of low energy are transformed into high energy ones. The most important attributes of efficient TTAUC are quantum yield ΦTTAUC, power density threshold I th (photon flux at which 50% of ΦTTAUC is achieved), and the upconversion shift of emitted photons (anti-Stokes shift). To date, approaches to balance these parameters have remained unclear. Herein, the cumulative effect of sensitizer triplet lifetime (τ0 S), sensitizer-annihilator triplet energy gap (ΔE T), and the total concentration of the sensitizer on the power density threshold at high TTAUC quantum yields is evaluated experimentally using Pt, Pd, and Zn tetraphenyl­porphyrin derivatives and a tetra-tert-butylperylene annihilator, and by kinetic rate modeling. The results suggest that a large energy gap (ΔE T ≥ 4 k B T) and long sensitizer triplet lifetime make the triplet–triplet energy transfer (TTET) extremely efficient and allow the utilization of high sensitizer concentrations for low I th. However, for large upconversion shifts, the triplet energy gap should be as small as possible. Smaller energy gap values result in slower forward TTET and faster reverse TTET, which together with high total sensitizer concentration can lead to a quenching of annihilator’s triplet state and therefore elevate the I th. In this regard, low concentration of a sensitizer is beneficial, making sensitizers with high molar extinction coefficients preferential. Sensitizers with a long living triplet state and a high molar extinction coefficient can work efficiently and have low I th at 0 k B T or even negative ΔE T. Kinetic rate modeling further helps to optimize the parameters for best possible TTAUC performance. Thus, the findings of the study pave the way for the design of TTAUC systems with superior performance, such as high ΦTTAUC at low excitation power densities with large anti-Stokes shift, for, for example, solar-driven photovoltaics, photocatalysis, bioimaging, and safe light-triggered drug-delivery systems.

A triplet–triplet annihilation upconversion of 24.5% was achieved at a remarkably low 600 μM annihilator concentration in a viscous polymer matrix.

The full potential of triplet fusion photon upconversion (TF-UC) of providing high-energy photons locally with low-energy excitation is limited in biomedicine and life sciences by its oxygen sensitivity. This hampers...