Time-resolved ESR studies on transient radicals photogenerated in solutions of melamine in ethylene glycol

Chemically Induced Dynamic Electron Polarization (CIDEP) spectra of transient radicals generated by laser pulse with λ = 248 nm in solutions of melamine in ethylene glycol have been studied by means of time-resolved (TR) ESR at room temperature. The main products are radicals of the solvent molecules formed through abstraction of hydrogen from ethylene glycol by excited melamine molecules and a melamine radical with attached hydrogen atom on melamine. Parameters obtained from well resolved TR ESR spectra coincide with parameters of radical of ethylene glycol HOC{radical dot}HCH2OH and methylol {radical dot}CH2OH, and an unresolved ESR spectrum was attributed to the melamine radical. The electron spin polarization results from the radical pair mechanism (RPM) involving S-T0 mixing (ST0M) and additionally from a small part of triplet mechanism (TM). In order to establish the possible structure and nature of melamine radical quantum-chemical calculations by the DFT B3LYP method using several different basis sets have been done. The reaction pathway and mechanisms of alcohol and melamine radicals formation are proposed and supported by DFT calculations within B3LYP and CIS(D) methods. Melamine and ethylene glycol free radicals relaxation time T2 was estimated as 1.5 and 0.5 μs, respectively. © 2005 Elsevier B.V. All rights reserved