Chemically induced dynamic electron polarization studies of a pH-dependent free radical cage formed in a photoinitiator labeled poly(methacrylic acid)

Time-resolved electron spin resonance (TR-ESR) has been used to investigate the effect of pH-dependent poly(methacrylic acid) clustering on the radical pair generated from photolysis of a poly(methacrylic acid) acid sample randomly labeled with the common a-hydroxy ketone photoinitiator 1. The TR-ESR spectra for the ketyl radical show a dramatic change in electron spin polarization mechanism, from a predominantly triplet mechanism (TM) at low pH (below 6) to a predominantly radical pair mechanism (RPM) at high pH (above 7). The ratio of RPM/TM polarization exhibits a sigmoidal behavior as a function of pH which passes through an inflection point at pH 6.9 ± 0.1. The inflection point agrees well with previous estimates for pH-dependent cluster opening in poly(methacrylic acid). These results indicate that the pH-dependent cluster is capable of forming a cage around the geminate radical pair which restricts its motion at low pH. At higher pH, the cluster opens, allowing the ketyl radical to escape the pair. Studies of the benzoyl partner in the radical pair, which is attached covalently to the polymer backbone, indicate differing environments within the cluster even at pH below cluster opening'. This study represents the first application of TR-ESR and electron spin polarization (ESP) to the problem of pH-dependent clustering and reveals new features of the pH-dependent poly(methacrylic acid) cluster.