Size economy and first hyperpolarizability: synthesis and nonlinear optical behavior of ferrocene-based donor-acceptor chromophores lacking π-linkers.

The question of size economy in the design of chromophores for nonlinear optics is addressed in this investigation. We have synthesized directly linked donor-acceptor dyads, which lack a π-conjugated linker, the presence of which is usually considered obligatory in materials designed for nonlinear optics. Correlating linear optical data, electrochemical data, computational data and hyper Rayleigh scattering (HRS) data on ferrocene (Fc) based dyads, we demonstrate that the first hyperpolarizability of such size economical chromophores is significantly better compared to that of Fc based, traditional, larger, donor-π-acceptor chromophores. Arguably, a larger π-conjugated linker decreases the electronic communication between the donor and the acceptor and weakens the intramolecular charge transfer in such chromophores.