Achieving Symmetry-Breaking Charge Separation in Perylenediimide Trimers: The Effect of Bridge Resonance.
Kangwei WangGuangwei ShaoShaoqian PengXiaoxiao YouXingyu ChenJingwen XuHuaxi HuangHuan WangDi WuJian-Long XiaPublished in: The journal of physical chemistry. B (2022)
Symmetry-breaking charge separation (SB-CS) provides a very promising option to engineer a novel light conversion scheme, while it is still a challenge to realize SB-CS in a nonpolar environment. The strength of electronic coupling plays a crucial role in determining the exciton dynamics of organic semiconductors. Herein, we describe how to mediate interchromophore coupling to achieve SB-CS in a nonpolar solvent by the use of two perylenediimide (PDI)-based trimers, 1,7-tri-PDI and 1,6-tri-PDI . Although functionalization at the N-atom decreases electronic coupling between PDI units, our strategy takes advantage of " bridge resonance ", in which the frontier orbital energies are nearly degenerate with those of the covalently linked PDI units, leading to enhanced interchromophore electronic coupling. Tunable electronic coupling was realized by the judicious combination of " bridge resonance " with N -functionalization. The enhanced mixing between the S 1 state and CT/CS states results in direct observation of the CT band in the steady-state UV-vis absorption and negative free energy of charge separation (Δ G CS ) in both chloroform and toluene for the two trimers. Using transient absorption spectroscopy, we demonstrated that photoinduced SB-CS in a nonpolar solvent is feasible. This work highlights that the use of " bridge resonance " is an effective way to control exciton dynamics of organic semiconductors.