A combined first principles TDDFT and experimental study on the UV-Vis spectra properties of M(p-nitrophenyl azo resorcinol)3 complexes (M: Fe, Cr)

Authors : Tuğba TÜĞSÜZ ARİFİOĞLU, Melis EFE ÇINAR, Nuray ŞATIROĞLU

Pages : 99-108

Doi:10.3906/kim-1212-39

View : 12 | Download : 3

Publication Date : 0000-00-00

Article Type : Research Paper

Abstract :UV-Vis absorption data of p-nitrophenyl azo resorcinol insert ignore into journalissuearticles values(Magneson I); and its 2 Feinsert ignore into journalissuearticles values(III); and Crinsert ignore into journalissuearticles values(III); complexes were investigated both experimentally and theoretically. The geometries were optimized at BP86/TZVP level. The most stable spin states were computed as doublet and quartet for Feinsert ignore into journalissuearticles values(magneson);3 and Crinsert ignore into journalissuearticles values(magneson);3 complexes, respectively. Time-dependent density functional theory insert ignore into journalissuearticles values(TDDFT); was employed to explore the absorption spectra properties, whereas the solvent effects were taken into account using the polarizable continuum model insert ignore into journalissuearticles values(PCM);. The M06, B3LYP, and PBE0 hybrid functionals together with TZVP/LANL2TZ basis sets were used for comparing the results with experimental data. The theoretical analysis of electronic structure and molecular orbitals demonstrated that the low-lying absorption bands in the UV-Vis spectra are mainly p \to d ligand-to-metal charge transfer insert ignore into journalissuearticles values(LMCT); transition and p \to p ligand-to-ligand charge transfer insert ignore into journalissuearticles values(LLCT); transition for Feinsert ignore into journalissuearticles values(magneson);3, and, in addition to that of LMCT and LLCT, d \to p metal-to-ligand charge transfer insert ignore into journalissuearticles values(MLCT); transition for Crinsert ignore into journalissuearticles values(magneson);3 complexes. The good agreement between the experimental and TDDFT calculation, especially M06 and B3LYP absorption spectra of the metal Magneson I complexes, allowed us to provide a detailed estimation of the main spectral features of ferric and chromic complexes.
Keywords : p Nitrophenyl azo resorcinol, Magneson I, iron III, , chromium III, , DFT, TDDFT