Resolving the Multiple Emission Centers in Carbon Dots: From Fluorophore Molecular States to Aromatic Domain States and Carbon-Core States.

Despite many efforts focused on the emission origin of carbon dots (CDs), it is still a topic of debate. This is mainly due to the complex structure of these nanomaterials. Here, we developed an innovative method to evaluate the number and spectral characterizations of various emission centers in CDs. We monitored the photostability of a series of column-separated CDs under UV irradiation to obtain three-dimensional data sets and resolve them using multivariate decomposition methods. The obtained results clearly revealed the presence of three different types of emission centers in CDs, including molecular states, aromatic domain states, and carbon-core states so that their single or coexisting appearance was found to be deeply dependent on the reaction temperature. Furthermore, density functional theory and time-dependent density functional theory were used to investigate the electronic and optical properties of some different aza-polycyclic and corannulene molecules as possible polycyclic aromatic hydrocarbons responsible for the above-mentioned aromatic domain states.