期刊
JOURNAL OF CHEMICAL PHYSICS
卷 153, 期 22, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/5.0025224
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资金
- NSFC [U21001222, 21673031, 21761142005, 21911530095]
- State Key Laboratory of Fine Chemicals [ZYTS201901]
We prepared a series of compact Bodipy-anthryl electron donor/acceptor triads and dyads by attaching anthryl moieties at the 3-,5-positions of the Bodipy core, with a novel conformation restriction approach, to study the spin-orbit charge transfer intersystem crossing (SOCT-ISC). The conformation restrictions are imposed by the BF2 unit of Bodipy without invoking the previously reported method with 1,7-dimethyl or 1,3-dimethyl groups. Our new approach shows a few advantages, including the stronger electron accepting ability of the methyl-free Bodipy core (reduction potential anodically shifted by +0.3 V vs the methylated Bodipy), red-shifted absorption (by 21 nm), and longer triplet state lifetime (372 mu s vs 126 mu s). The effects of the different mutual orientations of the electron donor and acceptor on ultraviolet-visible absorption, fluorescence, triplet state quantum yields, and lifetimes were studied. Triads with orthogonal geometries show higher singlet oxygen quantum yields (Phi (Delta) = 37%) than those with more coplanar geometries. Since the non-radiative decay for the S-1 state is significant in the parent Bodipy chromophore (Phi (F) = 6.0%), we propose that in dyads/triads, the charge separation and recombination-induced ISC outcompete the non-radiative decay to the ground state, which is new in the study of SOCT-ISC. Density functional theory computation indicated a shallow torsion potential energy curve as compared to the meso-anthryl-Bodipy dyad analog, which may contribute a low triplet state quantum yield of the new dyads/triads. Triplet-triplet annihilation upconversion was performed with the electron donor/acceptor dyads as the triplet photosensitizer, with an upconversion quantum yield of 12.3%.
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