The Role of Methyl Groups in the Early Stage of Thermal Polymerization of Polycyclic Aromatic Hydrocarbons Revealed by Molecular Imaging

28 December 2020, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


The initial thermal reactions of aromatic hydrocarbons are relevant to many industrial applications. However, tracking the growing number of heavy polycyclic aromatic hydrocarbon (PAH) products is extremely challenging because many reactions are unfolding in parallel from a mixture of molecules. Herein, we studied the reactions of 2,7-dimethylpyrene (DMPY) to decipher the roles of methyl substituents during mild thermal treatment. We found that the presence of methyl substituents is key for reducing the thermal severity required to initiate chemical reactions in natural molecular mixtures. A complex mixture of thermal products including monomers, dimers, and trimers were characterized by NMR, mass spectrometry and non-contact atomic force microscopy (nc-AFM). A wide range of structural transformations including methyl transfer and polymerization reactions were identified. A detailed mechanistic understanding was obtained on the roles of H radicals during the polymerization of polycyclic aromatic hydrocarbons.


polycyclic aromatic hydrocarbon (PAH)
methyl transfer,
ipso attack by hydrogen atoms
noncontact AFM data

Supplementary materials

Supporting information


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