期刊
CHEMPHYSCHEM
卷 23, 期 8, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.202100912
关键词
electron spin polarization; perylene; radical-enhanced intersystem crossing; spin-spin exchange; triplet state
资金
- NSFC [U2001222, 21761142005, 21911530095]
- State Key Laboratory of Fine Chemicals
- RAS
- Ministry of Education and Science of the Russian Federation [075-15-2021-623]
- FRC Kazan Scientific Center of RAS
- European Union's Horizon 2020 Research and Innovation Program [871124]
- Dalian University of Technology [DUT18GJ205]
Attaching stable radicals to organic chromophores is an effective method to enhance the intersystem crossing (ISC) of the chromophores. The study investigated the effect of the radical on the photophysical properties of perylene and observed strong fluorescence quenching due to radical enhanced ISC. The interaction between the radical and the chromophore was found to be ferromagnetic based on DFT computations, with a calculated energy value of 0.05 to 0.10 eV.
Attaching stable radicals to organic chromophores is an effective method to enhance the intersystem crossing (ISC) of the chromophores. Herein we prepared perylene-oxoverdazyl dyads either by directly connecting the two units or using an intervening phenyl spacer. We investigated the effect of the radical on the photophysical properties of perylene and observed strong fluorescence quenching due to radical enhanced ISC (REISC). Compared with a previously reported perylene-fused nitroxide radical compound (triplet lifetime, tau(T)=0.1 mu s), these new adducts show a longer-lived triplet excited state (tau(T)=9.5 mu s). Based on the singlet oxygen quantum yield (phi(Delta)=7 %) and study of the triplet state, we propose that the radical enhanced internal conversion also plays a role in the relaxation of the excited state. Femtosecond fluorescence up-conversion indicates a fast decay of the excited state (<1.0 ps), suggesting a strong spin-spin exchange interaction between the two units. Femtosecond transient absorption (fs-TA) spectra confirmed direct triplet state population (within 0.5 ps). Interestingly, by fs-TA spectra, we observed the interconversion of the two states (D-1 <-> Q(1)) at similar to 80 ps time scale. Time-resolved electron paramagnetic resonance (TREPR) spectral study confirmed the formation of the quartet sate. We observed triplet and quartet states simultaneously with weights of 0.7 and 0.3, respectively. This is attributed to two different conformations of the molecule at excited state. DFT computations showed that the interaction between the radical and the chromophore is ferromagnetic (J>0, 0.05 similar to 0.10 eV).
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