Boron dipyrromethene (Bodipy) is one of the most extensively investigated organic chromophores. Most of the investigations are focused on the singlet excited state of Bodipy, such as fluorescence. In stark contrast, the study of the triplet excited state of Bodipy is limited, but it is an emerging area, since the triplet state of Bodipy is tremendously important for several areas, such as the fundamental photochemistry study, photodynamic therapy (PDT), photocatalysis and triplet-triplet annihilation (TTA) upconversion. The recent developments in the study of the production, modulation and application of the triplet excited state of Bodipy are discussed in this review article. The formation of the triplet state of Bodipy upon photoexcitation, via the well known approach such as the heavy atom effect (including I, Br, Ru, Ir, etc.), and the new methods, such as using a spin converter (e.g. C60), charge recombination, exciton coupling and the doubly substituted excited state, are summarized. All the Bodipy-based triplet photosensitizers show strong absorption of visible or near IR light and the long-lived triplet excited state, which are important for the application of the triplet excited state in PDT or photocatalysis. Moreover, the methods for switching (or modulation) of the triplet excited state of Bodipy were discussed, such as those based on the photo-induced electron transfer (PET), by controlling the competing Förster-resonance-energy-transfer (FRET), or the intermolecular charge transfer (ICT). Controlling the triplet excited state will give functional molecules such as activatable PDT reagents or molecular devices. It is worth noting that switching of the singlet excited state and the triplet state of Bodipy may follow different principles. Application of the triplet excited state of Bodipy in PDT, hydrogen (H2) production, photoredox catalytic organic reactions and TTA upconversion were discussed. The challenges and the opportunities in these areas were briefly discussed.

We report molecular designing strategies to enhance the effective visible-light absorption of cyclometalated Ir(III) complexes. Cationic cyclometalated Ir(III) complexes were prepared in which boron-dipyrromethene (Bodipy) units were attached to the 2,2'-bipyridine (bpy) ligand via -C≡C- bonds at either the meso-phenyl (Ir-2) or 2 position of the π core of Bodipy (Ir-3). For the first time the effect of π conjugating (Ir-3) or tethering (Ir-2) of a light-harvesting chromophore to the coordination center on the photophysical properties was compared in detail. Ir(ppy)2(bpy) (Ir-1; ppy = 2-phenylpyridine) was used as model complex, which gives the typical weak absorption in visible range (ε < 4790 M(-1) cm(-1) in region > 400 nm). Ir-2 and Ir-3 showed much stronger absorption in the visible range (ε = 71,400 M(-1) cm(-1) at 499 nm and 83,000 M(-1) cm(-1) at 527 nm, respectively). Room-temperature phosphorescence was only observed for Ir-1 (λ(em) = 590 nm) and Ir-3 (λ(em) = 742 nm). Ir-3 gives RT phosphorescence of the Bodipy unit. On the basis of the 77 K emission spectra, nanosecond transient absorption spectra, and spin density analysis, we proposed that Bodipy-localized long-lived triplet excited states were populated for Ir-2 (τT = 23.7 μs) and Ir-3 (87.2 μs). Ir-1 gives a much shorter triplet-state lifetime (0.35 μs). Complexes were used as singlet oxygen ((1)O2) photosensitizers in photooxidation. The (1)O2 quantum yield of Ir-3 (ΦΔ = 0.97) is ca. 2-fold of Ir-2 (ΦΔ = 0.52). Complexes were also used as triplet photosensitizer for TTA upconversion; upconversion quantum yields of 1.2% and 2.8% were observed for Ir-2 and Ir-3, respectively. Our results proved that the strong absorption of visible light of Ir-2 failed to enhance production of a triplet excited state. These results are useful for designing transition metal complexes that show effective strong visible-light absorption and long-lived triplet excited states, which can be used as ideal triplet photosensitizers in photocatalysis and TTA upconversion.

It is well-known that the fluorescence of a chromophore can be efficiently quenched by the free rotor effect, sometimes called intramolecular rotation (IMR), i.e. by a large-amplitude torsional motion. Using this effect, aggregation induced enhanced emission (AIE) and fluorescent molecular probes for viscosity measurements have been devised. However, the rotor effect on triplet excited states was rarely studied. Herein, with molecular rotors of Bodipy and diiodoBodipy, and by using steady state and timeresolved transient absorption/emission spectroscopies, we confirmed that the triplet excited state of the Bodipy chromophore is not quenched by IMR. This is in stark contrast to the fluorescence (singlet excited state), which is significantly quenched by IMR. This result is rather interesting since a long-lived excited state (triplet, 276 μs) is not quenched by the IMR, but the short-lived excited state (singlet, 3.8 ns) is quenched by the same IMR. The unquenched triplet excited state of the Bodipy was used for triplet−triplet annihilation upconversion, and the upconversion quantum yield is 6.3%.