Details

Autor(en) / Beteiligte

• Liu, Dongyi
• El‐Zohry, Ahmed M.
• Taddei, Maria
• Matt, Clemens
• Bussotti, Laura
• Wang, Zhijia
• Zhao, Jianzhang
• Mohammed, Omar F.
• Di Donato, Mariangela
• Weber, Stefan

Titel

Long‐Lived Charge‐Transfer State Induced by Spin‐Orbit Charge Transfer Intersystem Crossing (SOCT‐ISC) in a Compact Spiro Electron Donor/Acceptor Dyad

Ist Teil von

• Angewandte Chemie (International ed.), 2020-07, Vol.59 (28), p.11591-11599

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2020

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (3CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the 3NI* state. Then the slow secondary CS (125 ns) gives the long‐lived 3CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1NI*→1CT→3NI*→3CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory. A rigid, simple, spiro compact electron donor/acceptor (D/A) dyad shows a long‐lived triplet charge transfer (3CT) state (0.94 μs) with a high energy level (ca. 2.12 eV), based on a new electron spin‐control method using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC) (1NI*→1CT→3NI*→3CT; NI=naphthalimide), without heavy atoms or chromophores with intrinsic intersystem crossing (ISC) ability.