Multi-heteroatom doped nanographenes: enhancing photosensitization capacity by forming an electron donor-acceptor architecture.

Abstract

Systematically tuning and optimizing the properties of synthetic nanographenes (NGs) is particularly important for NG applications in diverse areas. Herein, by devising novel electron donor-acceptor (D-A) type structures, we reported a series of multi-heteroatom-doped NGs possessing an electron-rich chalcogen and electron-deficient pyrimidine or pyrimidinium rings. Comprehensive experimental and theoretical investigations revealed significantly different physical, optical, and energetic properties compared to the non-doped HBC or chalcogen-doped, non-D-A analogues. Some intriguing properties of the new NGs such as unique electrostatically oriented molecular stacking, red-shifted optical spectra, solvatochromism, and enhanced triplet excitons were observed due to the formation of the D-A electron pattern. More importantly, these D-A type structures can serve as photosensitizers to generate efficiently reactive-oxygen species (ROS), and the structure-related photosensitization capacity that strengthens the electron transfer (ET) process leads to significantly enhanced ROS which was revealed by experimental and calculated studies. As a result, the cell-based photodynamic therapy (PDT) indicated that the cationic NG 1-Me+ is a robust photosensitizer with excellent water-solubility and biocompatibility.