| Mechanistic Study on Chemiluminescence of Chloranilic Acid by Co(II)-Mediated Fenton-like System | |
| Tang, Yi-Qi; Mao, Li; Zhu, Ben-Zhan; Liu, Ya-Jun | |
| 2021-03-19 | |
| Source Publication | JOURNAL OF ORGANIC CHEMISTRY
 |
| ISSN | 0022-3263 |
| Volume | 86Issue:6Pages:4472-4482 |
| Abstract | Reacting with H2O2, tetrachloro-1,4-benzoquinone (TCBQ) produces chemiluminescence (CL), but chloranilic acid (CA), the dihydroxylation product of TCBQ does not. However, an unprecedented strong CL generates from CA/H2O2 in the presence of Co(II). Why? We performed quantum chemical calculations on the entire reaction process of CA/H2O2 and CA/H2O2/Co(II) systems. The computational results indicate: for CA/H2O2 system, the reason leading to non-CL as: there is no free (OH)-O-center dot produced by CA/H2O2, which prevents the subsequent reaction from taking place; for CA/H2O2/Co(II) system, the chemical process resulting in the CL as: First, a neutral dioxetane is formed via six sequential reactions. Then, the neutral dioxetane decomposes to generate a neutral excited-state (S-1) product via a gradually reversible charge transfer initiated luminescence mechanism. A conical intersection of the ground and the S-1-state potential energy surfaces facilitates the production of the S-1-state product. Ultimately, the neutral S-1 -state product emits light as a practical light emitter. The key component for forming dioxetane and the following CL is the intrinsically generated (OH)-O-center dot, which is roaming around at the region of C-2 atoms of the CA moiety, instead of being free. The quantum chemical calculations supported the experimental observation and conclusion by providing the mechanistic explanation in detail. |
| Department | 环境化学与生态毒理学国家重点实验室 |
| WOS Research Area | Chemistry, Organic |
| Document Type | 期刊论文 |
| Identifier | https://ir.rcees.ac.cn/handle/311016/45772 |
| Collection | 环境化学与生态毒理学国家重点实验室 |
| Affiliation | 1.Beijing Normal Univ, Coll Chem, Key Lab Theoret & Computat Photochem, Minist Educ, Beijing 100875, Peoples R China 2.Chinese Acad Sci, Res Ctr Ecoenvironm Sci, State Key Lab Environm Chem & Ecotoxicol, Beijing 100085, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
| Recommended Citation GB/T 7714 | Tang, Yi-Qi,Mao, Li,Zhu, Ben-Zhan,et al. Mechanistic Study on Chemiluminescence of Chloranilic Acid by Co(II)-Mediated Fenton-like System[J]. JOURNAL OF ORGANIC CHEMISTRY,2021,86(6):4472-4482. |
| APA | Tang, Yi-Qi,Mao, Li,Zhu, Ben-Zhan,&Liu, Ya-Jun.(2021).Mechanistic Study on Chemiluminescence of Chloranilic Acid by Co(II)-Mediated Fenton-like System.JOURNAL OF ORGANIC CHEMISTRY,86(6),4472-4482. |
| MLA | Tang, Yi-Qi,et al."Mechanistic Study on Chemiluminescence of Chloranilic Acid by Co(II)-Mediated Fenton-like System".JOURNAL OF ORGANIC CHEMISTRY 86.6(2021):4472-4482. |
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