Electronic coupling and spin–orbit charge transfer intersystem crossing (SOCT-ISC) in compact BDP–carbazole dyads with different mutual orientations of the electron donor and acceptor

Abstract

In order to study the spin-orbit charge transfer induced intersystem crossing (SOCT-ISC), Bodipy (BDP)-carbazole (Cz) compact electron donor/acceptor dyads were prepared. Charge transfer (CT) emission bands were observed for dyads showing strong electronic coupling between the donor and the acceptor (coupling matrix elements V_DA, 0.06 eV-0.18 eV). Depending on the coupling magnitude, the CT state of the dyads can be either dark or emissive. Equilibrium between the ¹LE (locally excited) state and the ¹CT state was confirmed by temperature-dependent fluorescence studies. Efficient ISC was observed for the dyads with Cz connected at the meso-position of the BDP. Interestingly, the dyad with non-orthogonal geometry shows the highest ISC efficiency (Φ_Δ = 58%), which is different from the previous conclusion. The photo-induced charge separation (CS, time constant: 0.7 ps) and charge recombination (CR, ∼3.9 ns) were studied by femtosecond transient absorption spectroscopy. Nanosecond transient absorption spectroscopy indicated that the BDP-localized triplet state was exceptionally long-lived (602 µs). Using pulsed laser excited time-resolved electron paramagnetic resonance spectroscopy, the SOCT-ISC mechanism was confirmed, and we show that the electron spin polarization of the triplet state is highly dependent on the mutual orientation of the donor and acceptor. The dyads were used as triplet photosensitizers for triplet-triplet-annihilation (TTA) upconversion, and the quantum yield is up to 6.7%. TTA-based delayed fluorescence was observed for the dyads (τ_DF = 41.5 µs). The dyads were also used as potent photodynamic therapy reagents (light toxicity of IC₅₀ = 0.1 µM and dark toxicity of IC₅₀ = 70.8 µM).