Charge Transfer, Intersystem Crossing, and Electron Spin Dynamics in a Compact Perylenemonoimide-Phenoxazine Electron Donor-Acceptor Dyad

With phenoxazine (PXZ) as the electron donor and perylene-3,4-dicarboximide (PMI) as the electron acceptor, we prepared a compact, orthogonal electron donor-acceptor dyad (PMI-PXZ) to study the spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC). A weak charge transfer (CT) absorption band, due to S-0 -> (CT)-C-1 transition, was observed (epsilon = 2840 M-1 cm(-1) at 554 nm, FWHM: 2850 cm(-1)), which is different from that of the previously reported analogue dyad with phenothiazine as the electron donor (PMI-PTZ), for which no CT absorption band was observed. A long-lived triplet state was observed (lifetime tau(T) = 182 mu s) with nanosecond transient absorption spectroscopy, and the singlet oxygen quantum yield (Phi(Delta) = 76%) is higher than that of the previously reported analogue dyad PMI PTZ (Phi(Delta) = 57%). Ultrafast charge separation (ca. 0.14 ps) and slow charge recombination (1.4 ns) were observed with femtosecond transient absorption spectroscopy. With time-resolved electron paramagnetic resonance spectroscopy (TREPR), we confirmed the SOCT-ISC mechanism, and the electron spin polarization phase pattern of the triplet-state TREPR spectrum is (e, e, a, e, a, a), which is dramatically different from that of PMI PTZ (a, e, a, e, a, e), indicating that the triplet-state TREPR spectrum of a specific chromophore in the electron donor-acceptor dyads is not only dependent on the geometry of the dyads but also dependent on the structure of the electron donor (or acceptor). Even one-atom variation in the donor structure may cause significant influence on the electron spin selectivity of the ISC of the electron donor-acceptor dyads.