Fluorescence Solvatochromism of Carbon Dot Dispersions Prepared from Phenylenediamine and Optimization of Red Emission

Fluorescent carbon dots (CDs) are of interest as a promising alternative to quantum dots, partly because they do not include heavy metals. However, most CDs exhibit blue or green emission, while red-emitting CDs are required for a variety of applications. In the present work, CDs were synthesized by refluxing three phenylenediamine (PD) isomers with amino groups at different positions (o-PD, m-PD, and p-PD) in diphenyl ether at 250 °C for 4 h. Upon dispersing the resulting CDs in eight solvents with different polarities, emission colors ranging from green to red were observed. Among these CDs, p-PD-derived CDs exhibited both the longest emission wavelength range, from 538 to 635 nm, and the highest absolute red photoluminescence quantum yield (PLQY) of 15%. Herein the results are discussed based on a comparison of the polymerization processes of o-PD, m-PD, and p-PD. This work demonstrated that the optimum reaction time was 2 h, which yields a p-PD-derived CD dispersion in methanol with red emission and an absolute PLQY as high as 18%. Additionally, the use of 1-decanol and deuterated methanol in place of methanol improved the maximum absolute PLQY to 25% and 36%, respectively. These improved values are attributed to reduced concentration quenching by suppression of π-π stacking interactions and inhibition of the nonradiative relaxation process through the vibration of OH groups, respectively.