Theoretical study on the effect of different π-linker on the performance of sensitizer in carbazole-based dyes

Derived from diarylamine sensitizer diphenyl-(7-pyridin-4-yl-9H-carbazol-2-yl)-amine (N13), a series of novel D[Formula: see text]A carbazole-based organic dye sensitizers with different [Formula: see text]-linkers were designed for searching more effective sensitizers in dye-sensitized solar cells (DSSCs) design. Optimized geometries, electronic structure, and other parameters, which can evaluate the performance of DSSCs effectively and intuitively, were theoretically calculated by density functional theory (DFT) and time-dependent DFT methods at the M06/6-31G(d,p) level. The results indicated that the maximum absorption wavelength of designed dye was red-shifted and the molar absorption coefficient ([Formula: see text]) became higher. This phenomenon can be explained by the modification of the [Formula: see text]-bridge. The simulated Ultraviolet–visible spectroscopy (UV-Vis) absorption spectrum showed that the designed N,N-diphenyl-7-(5-(7-(5-(pyridin-4-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)thiophen-2-yl)-9H-carbazol-2-amine (N22) dye presents the largest red-shifted absorption band and the designed (E)-N,N-diphenyl-7-(2-(5[Formula: see text]-(pyridin-4-yl)-[2,2[Formula: see text]-bithiophene]-5-yl)vinyl)-9H-carbazol-2-amine (N21) dye showed the largest [Formula: see text], both of them depicted a high short-circuit photocurrent density ([Formula: see text]. Meanwhile, the charge separation hampered by long [Formula: see text]-linkers was also observed. These results are helpful for designing new sensitizers and providing effective guiding to experimental synthesis.