Twisted BODIPY derivative: intersystem crossing, electron spin polarization and application as a novel photodynamic therapy reagent†

The photophysical properties of a heavy atom-free BODIPY derivative with a twisted pi-conjugated framework were studied. Efficient intersystem crossing (ISC quantum yield: 56%) and an exceptionally long-lived triplet state were observed (4.5 ms in solid polymer film matrix and 197.5 mu s in solution). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy and DFT computations confirmed the delocalization of the triplet state on the whole twisted pi-conjugated framework and the zero-field-splitting (ZFS) D parameter of D = -69.5 mT, which is smaller than that of 2,6-diiodoBODIPY (D = -104.6 mT). The electron spin polarization (ESP) phase pattern of the triplet state TREPR spectrum of the twisted BODIPY is (a, a, e, a, e, e), which is different from that of 2,6-diiodo BODIPY (e, e, e, a, a, a), indicating that the electron spin selectivity of the ISC of the twisted structure is different from that of the spin orbital coupling effect. According to the computed spin-orbit coupling matrix elements (0.154-1.964 cm(-1)), together with the matched energy of the S-1/T-n states, ISC was proposed to occur via S-1 -> T-2/T-3. The computational results were consistent with TREPR results on the electron spin selectivity (the overpopulation of the T-Y sublevel of the T-1 state). The advantage of the long-lived triplet state of the twisted BODIPY was demonstrated by its efficient singlet oxygen (O-1(2)) photosensitizing (phi(Delta) = 50.0%) even under a severe hypoxia atmosphere (pO(2) = 0.2%, v/v). A high light toxicity (EC50 = 1.0 mu M) and low dark toxicity (EC50 = 78.5 mu M) were observed for the twisted BODIPY, and thus the cellular studies demonstrate its potential as a novel potent heavy atom-free photodynamic therapy (PDT) agent.

Automated summary

The photophysical properties of a heavy atom-free BODIPY derivative with a twisted pi-conjugated framework were investigated, showing efficient intersystem crossing and a long-lived triplet state. The electron spin selectivity of the twisted structure was found to differ from that of the spin orbital coupling effect, with potential applications in photodynamic therapy demonstrated through efficient singlet oxygen photosensitizing.