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Quenching dynamics study on photoinduced excited triplet duroquinone by TEMPO in 1,2-propandiol

机译:TEMPO在1,2-丙二醇中光诱导激发的三重态醌醌的猝灭动力学研究。

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摘要

Chemically induced dynamic electron polarization (CIDEP) spectrum and transient absorptive spectrum are recorded in photolysis of duroquinone (DQ) in 1,2-propanodiol (PG). Durosemiquinone neutral radical DQH• and PG ketyl radical are produced through hydrogen transfer reaction from PG to 3DQ*. When stable radical TEMPO is added to DQ/PG solution, photolysis results in CIDEP on TEMPO, which can be interpreted as a quartet precursor radical-triplet pair mechanism (QP-RTPM). There is competition between PG and TEMPO to quench 3DQ*. The CIDEP intensity of DQH• decreases with the increase of TEMPO concentration. The quenching dynamics in photolysis of DQ/TEMPO/PG system is analyzed in detail. Based on the dynamics analysis and the measurement of the lifetime of 3DQ* by its transient absorbance decay, the quenching rate constant of 3DQ* by TEMPO in PG is obtained as 1.34 × 107 L mol−1 s−1. This quenching rate constant is closely diffusion-controlled.
机译:化学诱导的动态电子极化(CIDEP)光谱和瞬态吸收光谱记录在1,2-丙二醇(PG)中的duroquinone(DQ)的光解中。 Durosemiquinone中性自由基DQH •和PG酮基是通过PG到 3 DQ *的氢转移反应生成的。当将稳定的自由基TEMPO添加到DQ / PG溶液中时,光解作用在TEMPO上导致CIDEP,这可以解释为四重前体自由基-三重态对机制(QP-RTPM)。 PG和TEMPO之间存在竞争以淬灭 3 DQ *。 DQH •的CIDEP强度随着TEMPO浓度的增加而降低。详细分析了DQ / TEMPO / PG体系光解中的猝灭动力学。基于动力学分析并通过瞬态吸收衰减测量 3 DQ *的寿命,得到TEMPO在PG中对 3 DQ *的猝灭速率常数为1.34×10 7 L mol -1 s -1 。该猝灭速率常数受到扩散控制。

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