Electronic structure, topological analysis and spectroscopic properties of sandwich indenyl complexes of ruthenium: A theoretical study

Abstract

Abstract We present in this work the density functional theory (DFT) calculations of the electronic structure, topological analysis and spectroscopic properties on sandwich indenyl complexes of ruthenium (ŋ5-C9H7) RuL with L= (ŋ5-C9H7) 1 and (ŋ5-C5H5) 2 in the gas phase and in THF, CH2Cl2, MeCN solvents. Our theoretical study has shown that the energetic properties are better in the reduction rather than experimentally achieved oxidation. AIM topology approach confirm the existence of hapticity ŋ3 (Ru C bond (Cp2)) in 1 and hapticity ŋ5 (Ru C bond (Cp2)) in 2. The electronic delocalization increases in 1 with respect to 2 because of the presence of the benzene ring, this is shown by the HOMA and FLU values of this compound (HOMA\u202f=\u202f0.234 and FLU\u202f=\u202f0.933). The diagram of the orbitals molecular predicts that the oxidized compounds of 1 and 2 are energetically less stable than the reduced ones. Nevertheless, 1+2 has significant luminescence and a pronounced solvatochromic effect, given by the values of stokes shifts (37.72 in the gas phase and 43.81 in the THF solvent).