Synthesis, third-order nonlinear optical properties and theoretical analysis of vinylferrocene derivatives

• A series of vinylferrocene derivatives were synthesized.
• The third-order nonlinear optical properties were measured using femtosecond degenerate four-wave mixing.
• The energy of HOMO, LUMO, Egap, natural charge, and MOs are performed by DFT.

A series of vinylferrocene derivatives were synthesized from the reaction of ferrocenecarboxaldehyde, alcohol, and triphenylphosphonium bromide in a one-pot, solid-state reaction. Their third-order nonlinear optical (NLO) properties were evaluated in N,N-dimethylformamide at 800 nm using femtosecond degenerate four-wave mixing. The third-order NLO susceptibilities of the compounds were 2.55–3.78 × 10−13 esu. The second-order hyperpolarizabilities of the molecules were 2.42–3.60 × 10−31 esu. The response times were 51–98 fs. The energy of the Highest Occupied Molecular Orbital (HOMO), the Lowest Unoccupied Molecular Orbital (LUMO), the energy gap of the HOMO and LUMO (Egap), natural charge, and molecular orbitals are performed by the Density Function Theory (DFT). The DFT study showed that the third-order NLO properties were increased with the increasing electron-withdrawing ability in accordance with the decreasing Egap and the increasing charge transfer among the donor, π-bridge, and the acceptor. The experiment and theoretical results show that the vinylferrocene derivatives have potential nonlinear optical applications.