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5,10‐dihydro‐5,10‐dimethylphenazine (PZ) and boron dipyrromethene (Bodipy) were linked to prepare compact electron donor/acceptor dyads and triads. The effect of the molecular geometry on the UV‐Vis absorption, fluorescence and the spin‐orbit charge transfer intersystem crossing (SOCT‐ISC) efficiency were studied. Interestingly, a broad near‐IR charge transfer (CT) absorption band (centred at 670 nm) was observed for the dyad/triad showing more coplanar geometry. Triplet state formation was observed in low polar solvents for the triad with orthogonal geometry (triplet state quantum yield is 30 % and lifetime is τT=210 μs). Femtosecond transient absorption spectra indicated fast charge separation (CS, 2 ps) and slow charge recombination (CR, >1.5 ns). The low‐lying 3CT state of the dyads/triads in polar solvent (1.23 eV vs. the 1.65∼1.69 eV of the 3LE state) was confirmed by intermolecular triplet photosensitizing experiments and the spin density surface analysis. These results are useful for design of new broadband, near‐IR absorbing heavy atom‐free triplet photosensitizers. [ABSTRACT FROM AUTHOR]

Intersystem crossing (ISC) was observed for naphthalimide (NI)‐derived Tröger's base, and the ISC was confirmed to occur by a spin‐orbital charge‐transfer (SOCT) mechanism. Conventional electron donor/acceptor dyads showing SOCT‐ISC have semirigid linkers. In contrast, the linker between the two chromophores in Tröger's base is rigid and torsion is completely inhibited, which is beneficial for efficient SOCT‐ISC. Femtosecond transient absorption (TA) spectra demonstrated charge‐separation and charge‐recombination‐induced ISC processes. Nanosecond TA spectroscopy confirmed the ISC, and the triplet state is long‐lived (46 μs, room temperature). The ISC quantum yield is dependent on solvent polarity (8–41 %). The triplet state was studied by pulsed‐laser‐excited time‐resolved EPR spectroscopy, and both the NI‐localized triplet state and triplet charge‐transfer state were observed, which is in good agreement with the spin‐density analysis. The Tröger's base was confirmed to be a potent photodynamic therapy reagent with HeLa cells (EC50=5.0 nm). [ABSTRACT FROM AUTHOR]

• Novel orthogonal Bodipy-phenylethynyl anthracene dyad was prepared. • Triple excited-state equilibrium in a photosensitizer showing SOCT-ISC. • Efficient intersystem crossing was observed (Φ Δ = 95%) without heavy atom effect. • Efficient triplet-triplet annihilation upconversion was observed (Φ UC = 18.9%). Spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC) is a promising method to design heavy atom-free triplet photosensitizers (PSs). Herein, a new organic triplet PS, BDP-An (Bodipy-phenylethynyl anthracene dyad) has been synthesized and studied. In polar solvents, charge transfer (CT) emission band was observed, and the singlet oxygen quantum yield (Φ Δ) is up to 95%. From femtosecond transient absorption (fs TA) spectra, SOCT-ISC mechanism was verified, the charge separation (CS) time takes1.6 ps, the lifetime of charge recombination (CR) is 3.8 ns, moreover the triplet state of phenylethynyl anthracene was also observed. In nanosecond transient absorption (ns TA) spectra, long-lived triplet states (τ T =108 μs) were observed, which are delocalized on both parts of the dyad, i.e. there is a triplet excited-state equilibrium. This is the first report on the triplet excited-state equilibrium observed in an electron donor/acceptor dyad showing SOCT-ISC. With BDP-An as the triplet donor and perylene as the triplet acceptor, triplet-triplet annihilation upconversion (TTA UC) was performed, the upconversion quantum yield was up to 18.9%, and the lifetime of TTA-based delayed fluorescence was determined as 70.8 μs. [ABSTRACT FROM AUTHOR]