Mechanochemical Synthesis of Carbazole Isomer Phosphors

The 1H-benzo[f]indole (Bd[f]), a carbazole (Cz) isomer is first reported as the source of Cz-based phosphors in 2020. In this work, the novel carbazole isomers, 1H-benzo[g]indole (Bd[g]) based derivatives, are synthesized by a one-step solvent-free mechanical ball milling reaction, establishing a facile, efficient, and environmentally friendly method for the synthesis of new Cz isomer phosphorescent derivatives with high yields compared to previously reported multi-step solvent-based thermochemical synthesis routes of Bd[f] derivatives with low yields. Six Bd[g] derivatives with different substituents, namely OCH₃-Bd, In-Bd, Bn-Bd, F-Bd, Cl-Bd, and Br-Bd, are synthesized, which exhibit distinctly different single-crystal structures and phosphorescent properties. After irradiation with 365 nm UV light, Bd[g] derivatives-doped poly (methyl methacrylate) (PMMA) films exhibit photoactivated green room-temperature phosphorescence with ultra-long lifetimes up to 1.65 s. Interestingly, the phosphorescence is stable in seawater along with good bactericidal properties, which also provide new candidates for indole-based marine antifoulants. This study demonstrates that mechanical ball milling is an efficient method for the synthesis of benzoindole heterocycles. Bd[g], as new members of the benzoindole family, are new building units to construct carbazole isomer phosphorescent molecules besides Bd[f].