Diversified Excited‐State Relaxation Pathways of Donor–Linker–Acceptor Dyads Controlled by a Bent‐to‐Planar Motion of the Donor

Abstract Herein, we introduce the cyclic 8π‐electron (C8π) molecule N , N ′‐diaryl‐dihydrodibenzo[ a , c ]phenazine ( DPAC ) as a dual‐functional donor to establish a series of new donor–linker–acceptor (D–L–A) dyads DLA1 – DLA5 . The excited‐state bent‐to‐planar dynamics of DPAC regulate the energy gap of the donor, while the acceptors A1 – A5 are endowed with different energy gaps and HOMO/LUMO levels. As a result, the rate and efficiency of the excited‐state electron transfer vs. energy transfer can be finely harnessed, which is verified via steady‐state spectroscopy and time‐resolved emission measurements. This comprehensive approach demonstrates, for the first time, the manifold of excited‐state properties governed by bifunctional donor‐based D–L–A dyads, including bent‐to‐planar, photoinduced electron transfer (PET) from excited donor to acceptor (oxidative‐PET), fluorescence resonance energy transfer (FRET), bent‐to‐planar followed by electron transfer (PFET), and PET from donor to excited acceptor (reductive‐PET).