Comparative assessment of structure-property relationships of new Cu(II) complex in selected density functionals

In order to evaluate the structure-property relationships of Cu(II) complex by using DFT methods, the structure of the newly synthesized Cu(II) complex, [Cu(6-Brpic)₂(bpy)], was investigated by XRD, FTIR, UV-Vis, and fluorescence spectroscopic methods. In addition, Hirshfeld surface and NBO analyses were fulfilled to identify possible interactions in the intermolecular and coordination environment. The five different DFT methods (HCTH, M06L, TPSSTPSS, B3LYP, and CAM-B3LYP levels), having four different functionalities (the GGA, meta-GGA, hybrid-GGA, and range-separated hybrid), were carried out so as to investigate the structure-property relationship, considering the geometric parameters (bond lengths and angles), vibrational frequencies, electronic absorption wavelengths, electronic transitions, and linear and nonlinear optical parameters. The R² for structural and vibrational parameters, as well as MPD%, MAD, an optimal scaling factor (λ) and overall root mean square (RMS) deviation, were considered only at vibration frequencies. While it was determined that M06-L and TPSSTPSS levels gave the best results for the bond lengths and angles of the Cu(II) complex, the best results for vibrational frequencies were obtained in the HCTH method along with these methods. In NLO parameters, the static and dynamic first-order hyperpolarizability (<β(0;0,0)> and β(-ω;ω,0)/<β(-2ω;ω,ω)>) values, the largest values were obtained in the HCTH method (38.817 × 10^-30 and 437.86 × 10^-30/201.55 × 10^-30 esu), whereas the smallest values were found to be in the CAM-B3LYP/TPSSTPSS levels (6.118 × 10^-30 esu, 8.270 × 10^-30/11.730 × 10^-30 esu). By regarding the static γ (<γ(0;0,0,0)>) and dynamic (<γ(-ω;ω,0,0)> parameters, the largest values were calculated in the M06L (232.101 × 10^-36) and HCTH (1711.52 × 10^-36) methods and the smallest values were obtained in the CAM-B3LYP (43.281 × 10^-36 and 60.844 × 10^-36) method. In fact, it is obviously seen that the β and γ values obtained by the aforementioned DFT levels are many times higher than that of the standard molecule of urea. These results indicate that the Cu(II) complex may be used as a potential NLO material to evolve optoelectronic devices.