Citation: Heran Wang, Kai Chen, Shuo Fu, Haoxuan Wang, Jiaxuan Yuan, Xingyi Hu, Wenjuan Xu, Baoxiu Mi. Isomeric Bisbenzophenothiazines: Synthesis, Theoretical Calculations, and Photophysical Properties[J]. Acta Physico-Chimica Sinica, ;2024, 40(1): 230304. doi: 10.3866/PKU.WHXB202303047 shu

Isomeric Bisbenzophenothiazines: Synthesis, Theoretical Calculations, and Photophysical Properties

State Key Laboratory of Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, Nanjing 210023, China

Corresponding author: Wenjuan Xu, iamwjxu@njupt.edu.cn Baoxiu Mi, iambxmi@njupt.edu.cn
Received Date: 23 March 2023
Revised Date: 15 May 2023
Accepted Date: 17 May 2023
Available Online: 25 May 2023
Fund Project: the National Natural Science Foundation of China 21671109the Priority Academic Program Development of Jiangsu Higher Education Institutions PAPDthe Priority Academic Program Development of Jiangsu Higher Education Institutions YX030003

Phenothiazines (PTZs), have received a lot of attention for many optoelectronic applications, such as hole-transporting layers, functioning as host materials for organic light-emitting diodes; dye sensitizers in dye-sensitized solar cells; and hole-transporting materials for perovskite solar cells. However, studies on benzophenothiazine materials are limited. In this study, we synthesize three isomeric bis-benzophenothiazine compounds (D-PTZa, D-PTZb, and D-PTZc), all bearing an aromatic ring at the 1, 2-, 2, 3-, and 3, 4-positions, respectively. Next, we systematically investigate the relationship between their structures and properties and compare them with bis-phenothiazine compounds (D-PTZ). The highest occupied molecular orbital (HOMO) distributions for D-PTZb and D-PTZc are dispersed over benzophenothiazine moities, whereas the lowest unoccupied molecular orbitals (LUMOs) are localized at the middle phenyl- and naphthyl-groups, which are similar frontier orbital distribuitions to the D-PTZ case. For D-PTZa, the steric hindrance between the phenyl groups at the 1, 2- and middle positions increases, significantly distorting its spatial structure. Therefore, its HOMO and LUMO distributions differ from those of D-PTZb and D-PTZc. Notably, the HOMOs in D-PTZa are dispersed over the middle phenyl group and nitrogen atom, whereas the LUMOs are localized at the naphthyl group. The hole/electron excitation and frontier orbital analyses demonstrate that strong local π → π* transition mixing with weak charge transfer transition is responsible for the luminescence of D-PTZb and D-PTZc. Interestingly, the ultraviolet–visible absorption spectra of all samples exhibit strong π → π* transition absorption and weak n → π* transition absorption. Furthermore, the conjugated length of the molecule can be effectively increased with the introduction of an aromatic ring, resulting in a red-shift in the maximum absorption wavelength. Compared to D-PTZ, D-PTZa emits yellow-green light with a photoluminescence quantum efficiency (PLQE) of 14%. In addition, the introduction of a phenyl group at the 2, 3-position effectively stabilizes the HOMO energy level, slightly increasing its π → π* transition gap, while also emitting blue light with a PLQE of 1.7%. For D-PTZc, the introduction of a phenyl group at the 3, 4-position better linearizes the LUMO distribution, thereby stabilizing the LUMO energy level and reducing its π → π* transition gap. The maximum emission peak is observed at 520 nm, emitting yellow-green light with a PLQE of 13%. Overall, our molecular design and results on structure–property relationships can provide fundamental guidance for the design of phenothiazine derivatives with specific photoelectric performance.
- Benzophenothiazine,
- Organic optoelectronic materials,
- Density functional theory,
- Hole-electron analysis,
- Frontier molecular orbitals,
- Photophysical property
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