Title: Molecular quadratic non-linear optical properties of dipolar trans-tetraammineruthenium(II) complexes with pyridinium and thiocyanate ligands
Authors: Coe, BJ ×
Jones, LA
Harris, JA
Sanderson, EE
Brunschwig, BS
Asselberghs, Inge
Clays, Koen
Persoons, Andre #
Issue Date: Jan-2003
Publisher: Royal soc chemistry
Series Title: Dalton transactions issue:11 pages:2335-2341
Abstract: Seven new complex salts trans-[Ru-II(NCS)(NH3)(4)(L-A)][PF6](2) [L-A = N-methyl-4,4'-bipyridinium (MeQ(+)) 1, N-methyl-2,7-diazapyrenium (Medap(+)) 2, N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium (Mebpe(+))3, N-phenyl-4,4'-bipyridinium (PhQ(+))4, N-phenyl-4-[trans-2-(4-pyridyl) ethenyl] pyridinium (Phbpe(+))5, N-(4-acetylphenyl)- 4,4'bipyridinium (4-AcPhQ(+))6, or N-(2-pyrimidyl)-4,4'- bipyridinium (2-PymQ(+))7] have been prepared. The electronic absorption spectra of 1-7 display intense, visible metal- to- ligand charge- transfer (MLCT) bands, the energies (E-max) of which decrease in the order 2 > 1 > 3 > 4 > 6 > 5 > 7, as the electron-accepting ability of L-A increases. The E-max values generally correlate with cyclic voltammetric and H-1 NMR data. Comparisons of the MLCT absorption and electrochemical data for 1-7 show that a trans-{Ru-II (NCS)(NH3)(4)}(+) centre is a stronger electron donor than analogous groups containing only neutral ligands. Molecular rst hyperpolarizabilities have been measured by using the hyper- Rayleigh scattering technique with acetonitrile solutions and a 1064 nm laser, and static rst hyperpolarizabilities beta(0)[H] were obtained by application of the two- state model. Stark (electroabsorption) spectroscopic studies in butyronitrile glasses at 77 K have a orded dipole moment changes Deltamu(12) for the MLCT transitions which have been used to calculate beta(0)[S] values according to the two-state equation beta(0) = 3Deltamu(12)(mu(12))(2)/( E-max) (2) (mu(12) = transition dipole moment). Both the beta(0)[H] and beta(0) [S] data confirm that the increased electron donor ability of a trans-{Ru-II(NCS)(NH3)(4)}(+) centre affords enhanced beta(0) values, when compared with related complexes containing the neutral trans ligands NH3, 4-( dimethylamino)pyridine, N-methylimidazole (mim) or pyridine. However, the magnitude of the observed beta(0) increase with respect to the analogous mim complexes varies over a range of ca. 25- 120%, depending upon L-A.
ISSN: 1477-9226
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

Files in This Item:

There are no files associated with this item.

Request a copy


All items in Lirias are protected by copyright, with all rights reserved.

© Web of science