Bennett Yoonjae Cho
Princeton International School of Mathematics and Science
Abstract
Chemiluminescence based on peroxyoxalate reactions underlies the operation of commercial glowsticks, which are widely used as portable light sources. Despite their practical value, a major limitation is their relatively short emission duration, which is intrinsically governed by reaction kinetics. In this study, we investigated how structural variation of the oxalate ester affects emission dynamics by comparing bis(2,4,6-trichlorophenyl) oxalate (TCPO) and bis(2,4-dinitrophenyl) oxalate (DNPO). Under identical experimental conditions, DNPO exhibited a consistently longer emission duration than TCPO. This difference can be rationalized by the distinct steric and electronic properties of the substituents. TCPO introduces steric congestion through multiple chlorine atoms, while DNPO incorporates strongly electron-withdrawing nitro groups that extend π-resonance and slow the perhydrolysis step. These findings highlight that beyond external factors such as temperature and catalyst concentration, rational modification of oxalate ester structure provides a viable strategy for tuning the brightness–lifetime trade-off in glowsticks. Our results suggest that electronic and steric descriptors, including molar refractivity (MR) and topological polar surface area (TPSA), can serve as predictive tools for guiding the design of new oxalate esters with prolonged emission, thereby offering opportunities for improved chemiluminescent devices in both practical and fundamental contexts.
