Contrasting linear and quadratic nonlinear optical behavior of dipolar pyridinium chromophores with 4-(dimethylamino)phenyl or ruthenium(II) ammine electron donor groups.
In this article, we contrast the optical properties of dipolar chromophores having 4-(dimethylamino)phenyl electron donor (D) and pyridinium acceptor (A) groups with those of closely related cations having pyridyl-coordinated Ru(II) donors. A range of physical data, including that from Stark (electroabsorption) spectroscopy, permits unprecedented quantitative comparisons, most notably regarding the effects of extension of bridging polyene chains. The purely organic compounds display normal optical properties in that their intense, visible pi --> pi intramolecular charge-transfer (ICT) bands red-shift as the number of E-ethylene units (n) increases from 1 to 3 and the associated static first hyperpolarizabilities beta(0) increase steadily with n. The related Ru(II) complexes show intense, visible d --> pi metal-to-ligand charge-transfer (MLCT) bands, which are found to lower energy when compared with the ICT transitions of the corresponding organics. Abnormally, these MLCT bands blue-shift as n increases, and beta(0) maximizes at n = 2. Time-dependent density-functional theory and finite field calculations verify these empirical trends for both types of compound, which can be rationalized as arising from the differing orbital structures of the chromophores and the associated degrees of D-A electronic coupling.
Contribution from the Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK. b.coe@man.ac.uk
Benjamin J
BJ
Coe
James A
JA
Harris
Bruce S
BS
Brunschwig
Javier
J
Garín
Jesús
J
Orduna
Simon J
SJ
Coles
Michael B
MB
Hursthouse