Photoexcited Species Localize on Solvent-Accessible Fluorophore-Rich Domains inside Carbon Dots

Understanding the optical properties of luminescent carbon dots (CDs) at the electronic level is essential for engineering their light-responsive behavior. The localization of photoexcited species and the pathways of their de-excitation govern CD performance in sensing, bioimaging, and emerging photocatalytic applications. Yet, the underlying mechanisms remain unresolved. Here, we combine multiscale simulations with experiments on CDs synthesized from citric acid (CA) and ethylenediamine (EDA), precursors capable of forming the molecular fluorophore 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-α]pyridine-7-carboxylic acid (IPCA). All-atom molecular dynamics simulations in water reveal that CA–EDA oligomeric condensation products containing IPCA units spontaneously assemble into dynamic ~2 nm nanoparticles with amorphous internal structures and stacked domains reminiscent of those observed in transmission electron microscopy images of CDs. Time-dependent density functional theory (TD-DFT) calculations show that photoexcited carriers are generated in these domains and remain spatially distributed, not confined to the CD core. Quenching experiments with Hg²⁺ confirm their accessibility to the environment. We therefore propose a structural model of fluorophore-rich domains embedded in an amorphous carbonaceous matrix, explaining the quasi-spherical morphology and characteristic blue photoluminescence. This model provides a mechanistic basis for fluorescence sensing and photocatalysis and establishes a framework for rational design of CDs with tailored photophysical and catalytic properties.