Photoluminescence mechanisms of red-emissive carbon dots derived from non-conjugated molecules

Abstract

Red-emissive carbon dots (R-CDs) have been widely studied because of their potential application in tissue imaging and optoelectronic devices. At present, most R-CDs are synthesized by using aromatic precursors, but the synthesis of R-CDs from non-aromatic precursors is challenging, and the emission mechanism remains unclear. Herein, different R-CDs were rationally synthesized using citric acid (CA), a prototype non-aromatic precursor, with the assistance of ammonia. Their structural evolution and optical mechanism were investigated. The addition of NH₃·H₂O played a key role in the synthesis of CA-based R-CDs, which shifted the emission wavelength of CA-based CDs from 423 to 667 nm. Mass spectrometry (MS) analysis indicated that the amino groups served as N dopants and promoted the formation of localized conjugated domains through an intermolecular amide ring, thereby inducing a significant emission redshift. The red-emissive mechanism of CDs was further confirmed by control experiments using other CA-like molecules (e.g., aconitic acid, tartaric acid, aspartic acid, malic acid, and maleic acid) as precursors. MS, nuclear magnetic resonance characterization, and computational modeling revealed that the main carbon chain length of CA-like precursors tailored the cyclization mode, leading to hexatomic, pentatomic, unstable three/four-membered ring systems or cyclization failure. Among these systems, the hexatomic ring led to the largest emission redshift (244 nm, known for CA-based CDs). This work determined the origin of red emission in CA-based CDs, which would guide research on the controlled synthesis of R-CDs from other non-aromatic precursors.

Keywords: Aromatization; Carbon dots; Citric acid; Photoluminescence mechanism; Red-emissive; Structural analysis.