Syntheses, density functional and sparkle PM6 semi empirical theoretical studies of O,O′-dialkyl/alkylenedithiophosphate derivatives of tin(IV) phthalocyanine adducts

Abstract

Seven new PcSn [S2P(OR)2]2 and PcSn [S2P(OGO)2]2 tin complexes where Pc is phthalocynine, R = Et, n-Pr, ios-Pr and tert-Bu and G = CH2CMe2CH2, CH2CEt2CH2, and CMe2CMe2 were synthesized and characterized by elemental analyses, Molecular weight determinations, IR and 31P spectroscopy. A sudden novel PcSn [SP(OR)2O]2 where R = iso-Pr has been recovered upon the hydrolysis of the complex with R = iso-Pr during recrystallization. Microanalytical and 31P NMR data revealed a 1:2 metal-ligand (O,O′-dialkyl and alkylenedithiophosphate) molar ratio in all complexes. Geometries were fully optimized at the B3LYP functional where the basis sets used were specified as generic basis sets and geometrical structures and electronic properties of the complexes were evaluated. The optimized geometries were confirmed to be minima on the potential energy surfaces through frequency calculations. The validity of the employed level of theory has been established through comparison of the calculated geometrical parameters of 12 with their observed counterparts. Thermodynamic stabilities were assessed through energy calculations. Aromaticity indices, local softnesses and condensed Fukui Functions were evaluated utilizing the optimized geometries at the specified level of theory. The absorption spectra of the complexes have been established using ORCA2.9 package utilizing the predicted optimized wave functions. Complexes proved to have high electronic susceptibilities.