Syntheses and properties of two-dimensional charged nonlinear optical chromophores incorporating redox-switchable cis-tetraammineruthenium(II) centers.
In this article, we describe a series of new complex salts in which electron-donating cis-{Ru(II)(NH3)(4)}(2+) centers are connected to two electron-accepting N-methyl/aryl-pyridinium groups. These V-shaped complexes contain either monodentate 4,4'-bipyridyl-derived ligands or related chelates based on 2,2':4,4":4',4'''-quaterpyridyl and have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi metal-to-ligand charge-transfer bands. These experiments reveal that these dipolar pseudo-C(2v)chromophores exhibit two substantial components of the beta tensor, beta(zzz)and beta(zyy), with the difference between them being most marked for the nonchelated systems. Time-dependent density-functional theory and finite field calculations serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts.
Coe
Benjamin J
BJ
School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Harris
James A
JA
Jones
Lathe A
LA
Brunschwig
Bruce S
BS
Song
Kai
K
Clays
Koen
K
Garín
Javier
J
Orduna
Jesús
J
Coles
Simon J
SJ
Hursthouse
Michael B
MB