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Perylenebisimide (PBI)–phenothiazine (PTZ) and PBI–diphenylamine (DPA) dyads were prepared, with the PTZ or DPA as the electron donor and the 6-subsituted PBI unit as the electron acceptor. The dyads were designed in such a way that electronic coupling (magnitude is the matrix elements, VDAand VDA*) between the electron donor and acceptor is controlled by conformation restriction. The effects of the electronic coupling on UV–Vis absorption and emission were studied. More significant charge-transfer (CT) absorption and CT fluorescence emission bands were observed for dyads with smaller dihedral angles between the electron donor and acceptor, thus stronger electronic coupling (VDA= 3290 cm–1and VDA* = 4317 cm–1) was observed than those with larger dihedral angle, showing weaker coupling effect (VDA= 1210 cm–1and VDA* = 2770 cm–1). Triplet state production was observed only for PBI–DPAbut not for PBI–PTZdyads. With an intermolecular triplet photosensitizing method, the triplet state of PBI–PTZdyads was observed. The femtosecond transient absorption spectra confirmed the ultrafast charge separation (CS, 0.3 ps ∼ 0.6 ps) and slow charge recombination (CR, 130 ps ∼ 240 ps) process. These results indicate that the CR does not produce any triplet state in the PBI–PTZdyads, for instance by the expected spin–orbital charge transfer intersystem crossing (SOCT-ISC). We propose that the lack of triplet state production in PBI–PTZdyads is due to the large separation of the 1CT and the 3CT/3PBI states, and the orthogonal geometry and the CR are not exclusively sufficient criteria for SOCT-ISC. Our results on controlling the absorption, emission, and ISC by tuning the VDAmagnitudes between the donor and acceptor will be useful for molecular design of compact electron donor/acceptor dyads.

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 time-resolved 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%.