Journal
CHEMICAL SCIENCE
Volume 13, Issue 45, Pages 13426-13441Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2sc04258d
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Funding
- NSFC [U2001222]
- State Key Laboratory of Fine Chemicals
- Fundamental Research Funds for the Central Universities [DUT22LAB610]
- Department of Education of the Xinjiang Uyghur Autonomous Region (Tian-Shan Chair Professor)
- Ministry of Science and Higher Education of the Russian Federation [075-15-2020-779]
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Spiro rhodamine (Rho)-naphthalenediimide (NDI) electron donor-acceptor orthogonal dyads were prepared to generate a long-lived charge separation state based on the electron spin control approach, prolonging the lifetime of the charge separation state.
Spiro rhodamine (Rho)-naphthalenediimide (NDI) electron donor-acceptor orthogonal dyads were prepared to generate a long-lived charge separation (CS) state based on the electron spin control approach, i.e. to form the (CS)-C-3 state, not the (CS)-C-1 state, to prolong the CS state lifetime by the electron spin forbidden feature of the charge recombination process of (CS)-C-3 -> S-0. The electron donor Rho (lactam form) is attached via three sigma bonds, including two C-C and one N-N bonds (Rho-NDI), or an intervening phenylene, to the electron acceptor NDI (Rho-Ph-NDI and Rho-PhMe-NDI). Transient absorption (TA) spectra show that fast intersystem crossing (ISC) (< 120 fs) occurred to generate an upper triplet state localized on the NDI moiety ((NDI)-N-3*), and then to form the CS state. For Rho-NDI in both non-polar and polar solvents, a long-lived (CS)-C-3 state (lifetime tau = 0.13 mu s) and charge separation quantum yield (phi(CS)) up to 25% were observed, whereas for Rho-Ph-NDI (tau(T) = 1.1 mu s) and Rho-PhMe-NDI (tau(T) = 2.0 mu s), a low-lying (NDI)-N-3* state was formed by charge recombination (CR) in n-hexane (HEX). In toluene (TOL), however, CS states were observed for Rho-Ph-NDI (0.37 mu s) and Rho-PhMe-NDI (0.63 mu s). With electron paramagnetic resonance (EPR) spectra, weak electronic coupling between the Rho and NDI moieties for Rho-NDI was proved. Time-resolved EPR (TREPR) spectra detected two transient species including NDI-localized triplets (formed via SOC-ISC) and a (CS)-C-3 state. The CS state of Rho-NDI features the largest dipolar interaction (|D| = 184 MHz) compared to Rho-Ph-NDI (|D| = 39 MHz) and Rho-PhMe-NDI (|D| = 41 MHz) due to the smallest distance between Rho and NDI moieties. For Rho-NDI, the time-dependent e,a & RARR; a,e phase change of the CS state TREPR spectrum indicates that the long-lived CS state is based on the electron spin control effect.
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