Key Laboratory of Synthetic and Natural Functional Molecule of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an, P. R. China.
Phys Chem Chem Phys. 2020 Jul 22;22(28):15900-15907. doi: 10.1039/d0cp02103b.
In this study, combined time-resolved spectroscopies of femtosecond transient absorption, nanosecond transient absorption, and nanosecond time-resolved resonance Raman spectroscopies as well as DFT calculations were performed to unravel the photorelease reaction mechanism of anthraquinon-2-ylethyl-1,2-diol protected carbonyl compound (Aqe-diol-PPG). It was shown that the triplet state of Aqe-diol-PPG underwent a PCET process to form a xylylene intermediate. After the C-O bond cleavage, a diradical intermediate was generated, which further released the protected benzaldehyde with the by-product Aqe-diol. A comparison work suggested that Aqe-diol underwent a further photoredox reaction in aqueous solutions.
在这项研究中,我们结合飞秒瞬态吸收、纳秒瞬态吸收和纳秒时间分辨共振拉曼光谱以及密度泛函理论计算,揭示了蒽醌-2-乙-1,2-二醇保护羰基化合物(Aqe-diol-PPG)的光解反应机制。结果表明,Aqe-diol-PPG 的三重态经历了质子电子转移(PCET)过程,形成了二甲苯中间体。在 C-O 键断裂后,生成了双自由基中间体,进一步释放出保护的苯甲醛和副产物 Aqe-diol。一项比较工作表明,Aqe-diol 在水溶液中经历了进一步的光氧化还原反应。