Theoretical study by DFT of organometallic complexes based on metallocenes active in NLO.

This study is based on the valuation of a few model molecules. The objective of this research is focused on linear optical (LO) and nonlinear optical (NLO) enhancement of five organometallic molecules based on different metallocenes. These molecules were subjected to several calculations by different long-range functionals CAM-B3LYP, LC-BLYP, LC-wPBE, wB97X, M11, and the following three Minnesota functionals: M06-2X and M08-HX in comparison with the MP2 approach. Hence, the CAM-B3LYP functional gave the closest NLO values to the MP2 method. Second, molecule 3A based on nickelocene recorded the highest static (βtot) value which is 76.46 Χ 10-30 esu and 4803.4 Χ 10-30 esu under the laser wavelength λ = 532 nm. Third, intramolecular charge transfers (ICTs) of the molecules studied are all directed in both directions (donor to acceptor and vice versa). Finally, the specific solvent for molecules 2A and 3A is acetonitrile, and the maximum wavelengths obtained for the isolated or solvated molecule are all located in the near UV; the corresponding interval is between 250 and 395 nm. Graphical abstract.