Insights of the pH-dependent emission of carbon dots: a density functional theory study

Abstract The mechanism of luminescence in carbon dots has long been a topic of controversy, as accurately characterizing their structure has proven difficult. This has made it challenging to guide the design and synthesis of carbon dots, hindering the development of highly efficient fluorescent varieties. Understanding the mechanism and regulatory mechanisms of carbon dot luminescence at the molecular level is important not only from a theoretical perspective but also has practical value. Previous studies have suggested that the fluorescence emission wavelength of carbon dots can be altered by changing the pH of the carbon dot solution, but the mechanism behind this modulation is not yet fully understood. In this study, we used density functional theory calculations and excited state simulations with 2, 3-Diaminophenazine, a representative luminescent molecule found in molecular state luminescent carbon dots, to investigate the effect of protonation on the absorption and fluorescence emission spectra of carbon dots. We analyzed the electronic structure and spatial distribution of the luminescent molecules before and after protonation and found that the change in molecular dipole moment caused by protonation was responsible for the significant red shift in the fluorescence spectrum. To further verify our findings, we modified the substituted functional groups with different electron-pulling abilities in the corresponding luminescent molecules to modulate the molecular dipole. The results showed that the larger the dipole moment in the luminescent molecules with different substituted functional groups, the longer the fluorescence emission wavelength. Therefore, the protonation-induced change in molecular dipole is the main reason for the pH-dependent modulation of luminescence in molecular state luminescent carbon dots.