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Syntheses and properties of two-dimensional charged nonlinear optical chromophores incorporating redox-switchable cis-tetraammineruthenium(II) centers

Syntheses and properties of two-dimensional charged nonlinear optical chromophores incorporating redox-switchable cis-tetraammineruthenium(II) centers
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 ? ?* metal-to-ligand charge-transfer bands. These experiments reveal that these dipolar pseudo-C(2v)chromophores exhibit two substantial components of the ? tensor, ?(zzz)and ?(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.
hyper-rayleigh-scattering, effective core potentials, metal-to-ligand, molecular quadratic hyperpolarizabilities, 2nd-order polarizability tensor, ruthenium(ii) ammine complexes, schiff-base complexes, starkspectroscopy, organometallic complexes, trans-tetraammineruthenium(ii)complexes
0002-7863
4845-4859
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Jones, Lathe A.
03cfa57d-e5cd-4a6e-a353-5304a6d8cb77
Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Song, Kai
7ed09f21-3ab6-418e-97f4-1a9b2afb6a21
Clays, Koen
f13fe1bc-8c4d-463a-97e3-423523cf4f75
Garín, Javier
f5cbd1bc-13e1-4ede-9c55-60661bdc23ff
Orduna, Jesús
a5970325-d172-417e-b280-1a76ad1405e5
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Jones, Lathe A.
03cfa57d-e5cd-4a6e-a353-5304a6d8cb77
Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Song, Kai
7ed09f21-3ab6-418e-97f4-1a9b2afb6a21
Clays, Koen
f13fe1bc-8c4d-463a-97e3-423523cf4f75
Garín, Javier
f5cbd1bc-13e1-4ede-9c55-60661bdc23ff
Orduna, Jesús
a5970325-d172-417e-b280-1a76ad1405e5
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28

Coe, Benjamin J., Harris, James A., Jones, Lathe A., Brunschwig, Bruce S., Song, Kai, Clays, Koen, Garín, Javier, Orduna, Jesús, Coles, Simon J. and Hursthouse, Michael B. (2005) Syntheses and properties of two-dimensional charged nonlinear optical chromophores incorporating redox-switchable cis-tetraammineruthenium(II) centers. Journal of the American Chemical Society, 127 (13), 4845-4859. (doi:10.1021/ja0424124).

Record type: Article

Abstract

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 ? ?* metal-to-ligand charge-transfer bands. These experiments reveal that these dipolar pseudo-C(2v)chromophores exhibit two substantial components of the ? tensor, ?(zzz)and ?(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.

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More information

Published date: 6 April 2005
Keywords: hyper-rayleigh-scattering, effective core potentials, metal-to-ligand, molecular quadratic hyperpolarizabilities, 2nd-order polarizability tensor, ruthenium(ii) ammine complexes, schiff-base complexes, starkspectroscopy, organometallic complexes, trans-tetraammineruthenium(ii)complexes

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Local EPrints ID: 20759
URI: http://eprints.soton.ac.uk/id/eprint/20759
ISSN: 0002-7863
PURE UUID: ec5c58d1-3a2e-43c2-a179-fcfe03e60b76

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Date deposited: 03 Mar 2006
Last modified: 15 Jul 2019 19:25

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Contributors

Author: Benjamin J. Coe
Author: James A. Harris
Author: Lathe A. Jones
Author: Bruce S. Brunschwig
Author: Kai Song
Author: Koen Clays
Author: Javier Garín
Author: Jesús Orduna
Author: Simon J. Coles
Author: Michael B. Hursthouse

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