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

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 x 10(-13) esu. The second-order hyperpolarizabilities of the molecules were 2.42-3.60 x 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 (E-gap), natural charge, and molecular orbitals are performed by the Density Function Theory (OFT). The OFT study showed that the third-order NLO properties were increased with the increasing electron-withdrawing ability in accordance with the decreasing E-gap and the increasing charge transfer among the donor, pi-bridge, and the acceptor. The experiment and theoretical results show that the vinylferrocene derivatives have potential nonlinear optical applications. (C) 2013 Elsevier Ltd. All rights reserved.