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)(NH(3))(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.
Coe
Benjamin J
BJ
School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK. b.coe@man.ac.uk
Harries
Josephine L
JL
Helliwell
Madeleine
M
Jones
Lathe A
LA
Asselberghs
Inge
I
Clays
Koen
K
Brunschwig
Bruce S
BS
Harris
James A
JA
Garín
Javier
J
Orduna
Jesús
J