Lighting up the Electrochemiluminescence of Carbon Dots through Pre‐ and Post‐Synthetic Design

Carbon dots (CDs), defined by their size of less than 10 nm, are a class of photoluminescent (PL) and electrochemiluminescent (ECL) nanomaterials that include a variety of carbon‐based nanoparticles. However, the control of their properties, especially ECL, remains elusive and afflicted by a series of problems. Here, the authors report CDs that display ECL in water via coreactant ECL, which is the dominant mechanism in biosensing applications. They take advantage of a multicomponent bottom‐up approach for preparing and studying the luminescence properties of CDs doped with a dye acting as PL and ECL probe. The dependence of luminescence properties on the surface chemistry is further reported, by investigating the PL and ECL response of CDs with surfaces rich in primary, methylated, or propylated amino groups. While precursors that contribute to the core characterize the PL emission, the surface states influence the efficiency of the excitation‐dependent PL emission. The ECL emission is influenced by surface states from the organic shell, but states of the core strongly interact with the surface, influencing the ECL efficiency. These findings offer a framework of pre‐ and post‐synthetic design strategies to improve ECL emission properties, opening new opportunities for exploring biosensing applications of CDs.