化学发光
鲁米诺
光化学
化学
过氧化物
发光
光发射
激发态
脱质子化
单线态氧
电子转移
氧气
有机化学
材料科学
光电子学
离子
核物理学
物理
作者
Angelo Giussani,Pooria Farahani,Daniel Martínez‐Muñoz,Marcus Lundberg,Roland Lindh,Daniel Roca‐Sanjuán
标识
DOI:10.1002/chem.201805918
摘要
Abstract Light emission from luminol is probably one of the most popular chemiluminescence reactions due to its use in forensic science, and has recently displayed promising applications for the treatment of cancer in deep tissues. The mechanism is, however, very complex and distinct possibilities have been proposed. By efficiently combining DFT and CASPT2 methodologies, the chemiluminescence mechanism has been studied in three steps: 1) luminol oxygenation to generate the chemiluminophore, 2) a chemiexcitation step, and 3) generation of the light emitter. The findings demonstrate that the luminol double‐deprotonated dianion activates molecular oxygen, diazaquinone is not formed, and the chemiluminophore is formed through the concerted addition of oxygen and concerted elimination of nitrogen. The peroxide bond, in comparison to other isoelectronic chemical functionalities (−NH−NH−, −N − −N − −, and −S−S−), is found to have the best chemiexcitation efficiency, which allows the oxygenation requirement to be rationalized and establishes general design principles for the chemiluminescence efficiency. Electron transfer from the aniline ring to the OO bond promotes the excitation process to create an excited state that is not the chemiluminescent species. To produce the light emitter, proton transfer between the amino and carbonyl groups must occur; this requires highly localized vibrational energy during chemiexcitation.
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