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The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

Paper ID Volume ID Publish Year Pages File Format Full-Text
26663 43969 2013 10 PDF Available
Title
The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates
Abstract

Peroxyoxalate chemiluminescence (PO-CL) was investigated using eight oxalates with various phenol moieties and the distyrylbenzene (DSB) fluorophores with various substituents. The ρ-values in the Hammett correlation between the substituent constants (σp+) of the DSBs and the singlet chemiexcitation yields (ΦS) for the PO-CL reactions varied from −0.50 to −1.01 depending on the oxalate structure, and the reactive oxalates tended to afford the higher absolute ρ-values but with a few exceptions. Based on the CIEEL mechanism, these experimental observations suggest that the aryloxy groups still remain in the 1,2-dioxetanones (DOTs), which are the postulated high-energy intermediates, and control the electronic properties of DOTs as electron-acceptors. The LUMO energies of the DOTs calculated by the ab initio method with a B3LYP/6-31g(d) basis set reveal that the lower the DOT-LUMO energies, the higher the absolute ρ-values were provided for the corresponding oxalates, as predicted by the frontier molecular orbital (FMO) theory. Thus, the chemical species interacting with the DSBs would be not unitary and will be DOTs.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The Hammett correlation was applied to the distyrylbenzene (DSB) enhanced peroxyoxalate chemiluminescence of several aryl oxalates. ► The ρ-values of the Hammett correlation are related to the LUMO energies of the postulated 1,2-dioxetanones (DOTs). ► The frontier molecular orbital (FMO) theory predicts that the high-energy intermediates will be the DOTs rather than 1,2-dioxetanedione (DOD).

Keywords
Peroxyoxalate chemiluminescence; Hammett correlation; High-energy intermediate; Frontier molecular orbital theory
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The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 252, 15 January 2013, Pages 222–231
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
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Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
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