Anthrathiadiazole Derivatives: Synthesis, Physical Properties and Two‐photon Absorption

• Published in: Chemistry : a European journal 2021-07, Vol.27 (42), p.10898-10902
• Main Authors: Fan, Mingxuan, Chen, Guangsheng, Xiang, Yu, Li, Junbo, Yu, Xianglin, Zhang, Wenying, Long, Xueting, Xu, Liang, Wu, Jinjun, Xu, Ze, Zhang, Qichun
• Format: Article
• Language: English
• Subjects: Absorption; anthrathiadiazoles; azaacenes; Chemistry; Cycloaddition; Diketones; Photon absorption; Photons; Physical properties; Substitutes; synthons; Thiadiazoles; two-photon absorption
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202100307

Anthrathiadiazole is a key synthon for the construction of large azaacenes, however, the attachment of different substituents onto the skeleton of anthrathiadiazole is difficult but highly desirable because it could be easy to enrich the structures of azaacenes. Here, it is demonstrated that anthrathiadiazole derivatives with −Br, −CN, and −OCH3 groups could be easily constructed through a simple [4+2] cycloaddition reaction between a,a,a’,a’‐tetrabromo‐o‐xylenes derivatives and benzo[c][1,2,5]thiadiazole‐4,7‐dione. The structures of the as‐prepared compounds with different substituents were carefully characterized. Moreover, the basic physical properties of the as‐prepared anthrathiadiazole derivatives were fully investigated, where the cyano‐substituted derivative (BTH‐CN) has the highest stability and the methoxy‐substituted derivative (BTH‐OCH3) is easy to be oxidized. Moreover, the two‐photon absorption (TPA) characteristics of different anthrathiadiazoles are also studied by using the femtosecond Z‐scan technique. The results show that the fused anthrathiadiazole skeletons possess large TPA cross‐section values δ2 in the range of 3000–5000 GM, where the nature, position and strength of the substituted groups have strong effect on these values. Here, by using a simple [4+2] cycloaddition reaction between a,a,a’,a’‐tetrabromo o‐xylenes derivatives and benzo[c][1,2,5]thiadiazole‐4,7‐dione, the substituted anthrathiadiazoles with −Br, −CN, and −OCH3 groups could be easily constructed. The as‐obtained compounds display the two‐photon absorption, where their cross‐section values are strongly affected by the nature, position and strength of the substituted groups.