Abstract
Using the LC-DFT/M06 functional, we elucidate the structure-property relationship for the effect of electron-donating substituents on tuning the nonlinear optical (NLO) and optical properties of a series of pyrene-core (PY) arylamine derivatives. After successfully synthesizing N1,N1,N3,N3,N6,N6,N8,N8-octakis(4-methoxyphenyl)pyrene-1,3,6,8-tetraamine (PYOMe), its crystallographic data and photophysical properties were reported. By substituting/removing the terminal -OMe donors in PYOMe with groups with different electron donation abilities, we systematically designed novel derivatives with adjusted optical and NLO properties. Comparison between the obtained results and those of the prototypical NLO chromophore p-nitroaniline (pNA) were performed. The experimental data from PYOMe and pNA allowed us to validate the applied DFT functional among six tested functionals. Charge transfer descriptors, such as the charge transfer distance (D-CT), the amount of charge transferred (q(CT)), and dipole moment change (mu(CT)), and other indices (H and t) were investigated. The trend observed for the beta(tot) amplitudes was justified by the parameters in the two-level model and by the total term Delta mu f/Delta E-3 for two crucial transitions of the investigated systems. Our investigation reveals that substitution of these systems results in larger beta(tot) amplitudes compared to that of the unsubstituted system. However, their beta(tot) amplitudes are smaller than that of pNA, except that of PY substituted with phenoxy groups. Additionally, our results indicate that optimal combinations of the different (optical) parameters involved in two-level approximation affects the NLO properties of the systems under investigation to a larger extent.