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Published April 6, 2005 | Supplemental Material
Journal Article Open

Syntheses and Properties of Two-Dimensional Charged Nonlinear Optical Chromophores Incorporating Redox-Switchable cis-Tetraammineruthenium(II) Centers

Abstract

In this article, we describe a series of new complex salts in which electron-donating cis-{Ru^(II)(NH_3)_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 β have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer bands. These experiments reveal that these dipolar pseudo-C_(2v) chromophores exhibit two substantial components of the β tensor, β_(zzz) and β_(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.

Additional Information

© 2005 American Chemical Society. Received 17 December 2004. Published online 10 March 2005. Published in print 1 April 2005. We thank the EPSRC for support (Grants GR/M93864 and GR/R54293) and also the Fund for Scientific Research-Flanders (FWO-V, G.0297.04), the University of Leuven (GOA/2000/3), the Belgian Government (IUAP P5/3), MCyT-FEDER (BQU2002-00219), and Gobierno de Aragon-Fondo Social Europeo (P009-2001 and E39). This research was partially carried out at Brookhaven National Laboratory under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences. Dr. Kurt Wostyn is thanked for his assistance with some of the HRS measurements, and we are very grateful to Profs. David P. Shelton (UNLV) and Santo Di Bella (Università di Catania) for some helpful comments regarding the physical aspects of these studies.

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August 19, 2023
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