Systematic study of the structure-property relationship of a series of ferrocenyl nonlinear optical chromophores

A series of novel nonlinear optical (NLO) chromophores 1-4 incorporating the ferrocenyl (Fc) group as an electron donor and 2-dicyanomethylene-3-cyano-4- methyl-2,5-dihydrofuran (TCF) derivatives as electron acceptors are presented. The use of a constant Fc donor and varied acceptors and bridges makes it possible to systematically determine the contribution of the conjugated bridge and the acceptor strength to chromophore nonlinear optical activity. The X-ray crystal structures of all four chromophores allow for the systematic investigation of the structure-property relationship for this class of molecules. For example, the crystal structures reveal that both cyclopentadienyl groups in the ferrocenyl donor contribute to the electron donating ability. The first-order hyperpolarizabilities β of these chromophores, measured by hyper-Rayleigh scattering (HRS) relative to p-nitroaniline are reported. These β values are compared to those calculated by density functional theory (DFT). The excellent agreement between the theoretical and experimental β values demonstrates that a linear relation exists between the hyperpolarizability and the bond length alternation. An electrooptic coefficient, r₃₃, of ∼25 pm/V at 1300 nm, for compound 4, incorporated into a polymer matrix, is competitive with organic chromophores. Moreover, this r₃₃ is more than 30 times larger than the previously reported value for an organometallic chromophore in a poled polymer matrix. This work not only underscores the potential for Fc donor moieties, which have been underutilized, but also demonstrates that experimental characterization and theoretical simulations are now congruent, viable methods for assessing potential performance of NLO materials.