화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.124, No.45, 9360-9374, 2020
Long-Lived Local Triplet Excited State and Charge Transfer State of 4,4 '-Dimethoxy Triphenylamine-BODIPY Compact Electron Donor/Acceptor Dyads
The spin-orbit charge transfer intersystem crossing (SOCT-ISC) and the formation of a long-lived charge transfer (CT) state were studied with a series of 4,4'-dimethoxy triphenylamine-BODIPY compact electron donor/acceptor dyads. Different torsion freedoms were applied in the dyads to tune the electronic coupling between the donor and acceptor, and a red-shifted CT absorption band was observed for one dyad. The dyads show solvent polarity-dependent singlet oxygen photosensitizing ability (quantum yields 3%-79%). Nanosecond transient absorption spectra of the dyad in nonpolar solvent confirm the formation of triplet states. The intrinsic triplet state lifetime is up to 383 mu s (in fluid solution), which is much longer than that accessed with the heavy atom effect (276 mu s). Intermolecular triplet photosensitizing of the dyads in a polar solvent produces a long-lived (CT)-C-3 state (lifetime, tau(CT) = 8.0 mu s supported by the electron spin density surface analysis). The triplet state lifetime of the dyads doped in a Clear Flex 50 polymer film is exceptionally long (7.6-11.4 ms), and formation of a long-lived CT state (37 mu s) was observed. Triplet-triplet annihilation upconversion was performed with the electron donor/acceptor dyads used as the triplet photosensitizer and perylene used as the triplet acceptor; the upconversion quantum yield is up to 15.8%.