The formation and decomposition of firefly dioxetanone

• Published in: Chemical physics letters Vol. 506; no. 4; pp. 269 - 275
• Main Authors: Min, Chun-gang, Ren, Ai-min, Li, Xiao-na, Guo, Jing-fu, Zou, Lu-yi, Sun, Ying, Goddard, John D., Sun, Chia-chung
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 20-04-2011
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2011.01.064

The formation and decomposition mechanism of firefly dioxetanone (see figure) are studied by M06 method in the gas phase and PCM solvent model.
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► This work reports the formation mechanism of dioxetanone, firstly. ► For the decomposition, one reaction path is proposed for the first time. ► The solvent effects were considered by using the PCM model.
Firefly bioluminescence has attracted great attention for many years. Some details of the mechanism underlying firefly bioluminescence remain elusive. In this study the formation and decomposition reactions of firefly dioxetanone (DO) have been investigated in the gas phase and in a solvent model with an appropriate dielectric constant. Firefly DO is identified as a key intermediate. The formation of DO involves a stepwise reaction mechanism: first the formation of the four-membered ring on the singlet potential surface but not on the triplet and then the departure of the
PO
4
CH
3
2
-
group. For the decomposition of DO, two possible reaction paths are proposed, one of which is reported for the first time.