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- Title
Long‐Lived Charge‐Transfer State in Spiro Compact Electron Donor–Acceptor Dyads Based on Pyromellitimide‐Derived Rhodamine: Charge Transfer Dynamics and Electron Spin Polarization.
- Authors
Chen, Xi; Sukhanov, Andrey A.; Yan, Yuxin; Bese, Damla; Bese, Cagri; Zhao, Jianzhang; Voronkova, Violeta K.; Barbon, Antonio; Yaglioglu, Halime Gul
- Abstract
We observed a long‐lived charge transfer (CT) state in a novel orthogonal compact electron donor–acceptor dyads, with closed form of rhodamine (Rho) as electron donor and pyromellitimide (PI),or thionated PI, as electron acceptor. The two parts in the dyads are connected via a spiro quaternary carbon atom, thus the torsion between the donor and acceptor is completely inhibited, which is beneficial to reduce the reorganization energy and to exploit the Marcus inverted region effect to prolong the CT state lifetime. Femtosecond transient absorption spectra show that the charge separation is rather fast, while nanosecond transient absorption spectra confirmed the formation of long‐lived CT state (2.6 μs). Time‐resolved electron paramagnetic resonance (TREPR) spectra determined the spin multiplicity of the long living state and assigned it to a 3CT state. Replacement of an oxygen atom in the PI part with a sulfur atom favoring classical intersystem crossing processes, causes a consistently shortening of the lifetime of the 3CT state (0.29 μs).
- Subjects
CHARGE transfer; CHARGE exchange; POLARIZED electrons; ELECTRON spin; SPIN polarization; ELECTRON spin states
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 33, p1
- ISSN
0044-8249
- Publication type
Academic Journal
- DOI
10.1002/ange.202203758