Diversified Excited-State Relaxation Pathways of Donor-Linker-Acceptor Dyads Controlled by a Bent-to-Planar Motion of the Donor.
Angew Chem Int Ed Engl
; 59(42): 18611-18618, 2020 Oct 12.
Article
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| MEDLINE
| ID: mdl-32648281
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).
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MEDLINE
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En
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Angew Chem Int Ed Engl
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2020
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Article