Towards understanding the kinetic behaviour and limitations in photo-induced copper(i) catalyzed azide–alkyne cycloaddition (CuAAC) reactions. Issue 36 (2nd September 2016)

• Record Type: Journal Article
• Authors: El-Zaatari, Bassil M.; Shete, Abhishek U.; Adzima, Brian J.; Kloxin, Christopher J.
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 36(2016)
• Page Start: 25504
• Page End: 25511
• Publication Date: 2016-09-02
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c6cp04950h
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The kinetics of the photo-CuAAC reaction were studied in various systems (monofunctional and polymer), providing new mechanistic and behavioral insight. Abstract : The kinetic behaviour of the photo-induced copper(i ) catalyzed azide–alkyne cycloaddition (CuAAC) reaction was studied in detail using real-time Fourier transform infrared (FTIR) spectroscopy on both a solvent-based monofunctional and a neat polymer network forming system. The results in the solvent-based system showed near first-order kinetics on copper and photoinitiator concentrations up to a threshold value in which the kinetics switch to zeroth-order. This kinetic shift shows that the photo-CuAAC reaction is not susceptible from side reactions such as copper disproportionation, copper(i ) reduction, and radical termination at the early stages of the reaction. The overall reaction rate and conversion is highly dependent on the initial concentrations of photoinitiator and copper(ii ) as well as their relative ratios. The conversion was decreased when an excess of photoinitiator was utilized compared to its threshold value. Interestingly, the reaction showed an induction period at relatively low intensities. The induction period is decreased by increasing light intensity and photoinitiator concentration. The reaction trends and limitations were further observed in a solventless polymer network forming system, exhibiting a similar copper and photoinitiator threshold behaviour.