Thermal homolysis of biazafullerenyl, (C59N)2, has been studied by CW ESR in the temperature range 290-829 K. The room-temperature ESR spectrum consists of a single sharp narrow line whose intensity is consistent with the presence of a low concentration of defect spins (1 spin per 600 C59N units). Around 500 K, three sharp lines emerge on top of the impurity signal and are assigned to the 14N(I = 1) hyperfine spectrum with a hyperfine coupling constant, aiso = 3.60(1) G and a g-factor of 2.0004(2). The intensity of the observed 14N hyperfine spectrum directly measures the fraction of the C59N• radicals formed as the temperature increases, growing from ∼50 ppm at 516 K to ∼300 ppm at 740 K. The temperature evolution of this fraction allows us to extract an estimate of the binding energy as 7(1) kcal/mol. The high temperature treatment of the sample eventually results in the partial decomposition and formation of C60.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry