Molecular self-healing mechanisms between C60-fullerene and anthracene unveiled by Raman and two-dimensional correlation spectroscopy

Abstract

The self-healing polymer P(LMA-co-MeAMMA) crosslinked with C₆₀-fullerene has been studied by FT-Raman spectroscopy in combination with two-dimensional (2D) correlation analysis and density functional theory calculations. To unveil the molecular changes during the self-healing process mediated by the Diels–Alder equilibrium between 10-methyl-9-anthracenyl groups and C₆₀-fullerene different anthracene–C₆₀-fullerene adducts have been synthesized and characterized by time-, concentration- and temperature-dependent FT-Raman measurements. The self-healing process could be monitored via the C₆₀-fullerene vibrations at 270, 432 and 1469 cm⁻¹. Furthermore, the detailed analysis of the concentration-dependent FT-Raman spectra point towards the formation of anthracene–C₆₀-fullerene adducts with an unusual high amount of anthracene bound to C₆₀-fullerene in the polymer film, while the 2D correlation analysis of the temperature-dependent Raman spectra suggests a stepwise dissociation of anthracene–C₆₀-fullerene adducts, which are responsible for the self-healing of the polymer.