Unraveling aryl peroxide chemistry to enrich optical properties of single-walled carbon nanotubes

Harnessing the unique optical properties of chirality-enriched single-walled carbon nanotubes (SWCNTs) is the key to unlocking the application of SWCNTs in photonics. Recently, it has been discovered that chemical modification of SWCNTs greatly increases their potential in this context. Despite the dynamic progress in this area, the mechanism of the chemical modification of SWCNTs and the impact of the reaction conditions on the properties of the obtained functional nanomaterials remain unclear. In this study, we demonstrate how the reaction environment influences the observed fluorescence pattern of SWCNTs after modification with benzoyloxy radicals generated <i>in situ</i>. The obtained results reveal that each diacyl peroxide molecule can generate either one or two radicals by two different mechanisms, <i>i.e.</i>, induced or spontaneous decomposition. Through proper selection of the reactant concentration, process temperature, and solvent, we were able to activate one or both radical decay pathways. In addition, the choice of a solvent, such as tetrahydrofuran or acetonitrile, allowed drastic changes in the functionalization process. Consequently, the SWCNT surface was grafted with functional groups <i>via</i> C-C bonds using radicals derived from the solvent molecules instead of attaching an aromatic moiety from the reactant present in the system through the expected C-O linkage. Verification of the structure of the chemically bound functional groups through hydrolysis opens the route to further modification of SWCNT surfaces using the labile ester connection. By gaining a better understanding of the emergence and behavior of the generated radicals, we demonstrate the possibility of controlling the density of introduced defects, as well as the selectivity of the functionalization process. The identification of the underlying chemical pathways responsible for the functionalization of SWCNTs paves the way for the design of precise methods of SWCNT modification to adjust their photonic characteristics for specific applications.