Electronic and molecular structures and bulk second–order nonlinear optical properties of ferrocenyl ynones

摘要: Ferrocenyl ynones FcCOCCR (R = H, TMS, Ph) exhibit moderate second harmonic generation efficiencies in the solid state, whereas methyl analog proved inactive. Their molecular structures and crystal packings were determined by single X-ray diffraction, confirming that inactive compound crystallizes a centrosymmetric space group. The electronic of these compounds studied experimentally (cyclic voltammetry, absorption spectra) theoretically (DFT TD-DFT calculations). It appeared COCCR groups are stronger electron acceptors than propionyl (COCH2CH3) Furthermore, better stabilize metal-centred HOMO-2 to HOMO orbitals lateral chain-centred LUMO decrease HOMO-LUMO gaps. TDDFT calculation transitions revealed lower energy (LE) higher (HE) bands observed spectra under study have more pronounced metal-to-ligand charge transfer character for ferrocenyl propionylferrocene. calculated static quadratic hyperpolarizabililities range ∼3 − 6 × 10−30 esu.