Pentacyanoiron(II) as an electron donor group for nonlinear optics:: Medium-responsive properties and comparisons with related pentaammineruthenium(II) complexes

In this article, we describe a series of complex salts in which electron-rich {Fe-II(CN)(5)}(3-) centers are coordinated to pyridyl ligands with electron-accepting N-methyl/aryl-pyridinium substituents. These compounds have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d -> pi* metal-to-ligand charge-transfer (MLCT) bands. The relatively large static first hyperpolarizabilities, beta(0), increase markedly on moving from aqueous to methanol solutions, accompanied by large red-shifts in the MLCT transitions. Acidification of aqueous solutions allows reversible switching of the linear and NLO properties, as shown via both HRS and Stark experiments. Time-dependent density functional theory and finite field calculations using a polarizable continuum model yield relatively good agreement with the experimental results and confirm the large decrease in beta(0) on protonation. The Stark-derived beta(0) values are generally larger for related {Ru-II(NH3)(5)}(2+) complexes than for their {Fe-II(CN) (5)} (3-) analogues, consistent with the HRS data in water. However, the HRS data in methanol show that the stronger solvatochromism of the Fe-II complexes causes their NLO responses to surpass those of their Ru-II counterparts upon changing the solvent medium.