Unravelling the effect of anchoring groups on the ground and excited state properties of pyrene using computational and spectroscopic methods

Anchoring groups play an important role in dye sensitized solar cells (DSCs). In order to acquire a suitable anchoring group for DSCs, a deeper understanding of the effect of anchoring groups on the ground and excited state properties of the dye is significant. In this context, various anchoring group connected pyrene derivatives are successfully synthesized and well characterized by using H-1, C-13-NMR, FT-IR and EI-MS spectrometry. The anchoring groups employed are carboxylic acid, malonic acid, acrylic acid, malononitrile, cyanoacrylic acid, rhodanine and rhodanine-3-acetic acid. The optimized geometries, HOMO-LUMO energy gap, light harvesting efficiency (LHE) and electronic absorption spectra of these dyes are studied by using density functional theory (DFT) calculations. The results show that pyrene connected with anchoring groups with weak electron pulling strength (PC, PAC and PMC) has a larger HOMO-LUMO energy gap, whereas that connected with anchoring groups with strong electron pulling strength (PCC, PMN, PR and PRA) has a reduced HOMO-LUMO energy gap. These molecules with a reduced energy gap are primarily preferred for DSC applications. Moreover, P, PC, PAC and PMC molecules undergo pi - pi* transition, whereas PCC, PMN, PR and PRA molecules show significant charge transfer along with pi - pi* transition. UV-visible absorption spectral studies on these dyes reveal that connecting various anchoring groups with different electron pulling abilities enables the pyrene chromophore to absorb in the longer wavelength region. Notably, an efficient bathochromic shift is observed for PCC, PMN, PR and PRA molecules in both electronic absorption and fluorescence spectral measurements, which suggests that the excitation is delocalized throughout the entire p-system of the molecules. Both theoretical and spectral studies reveal that dyes with an ICT character (PCC, PMN, PR and PRA) are suitable for dye sensitized solar cell applications.