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Combining Very Large Quadratic and Cubic Nonlinear Optical Responses in Extended, Tris-Chelate Metallochromophores with Six π-Conjugated Pyridinium Substituents

Coe, Benjamin J. and Fielden, John and Foxon, Simon P. and Brunschwig, Bruce S. and Asselberghs, Inge and Clays, Koen and Samoc, Anna and Samoc, Marek (2010) Combining Very Large Quadratic and Cubic Nonlinear Optical Responses in Extended, Tris-Chelate Metallochromophores with Six π-Conjugated Pyridinium Substituents. Journal of the American Chemical Society, 132 (10). pp. 3496-3513. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20100408-153120348

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Abstract

We describe a series of nine new complex salts in which electron-rich Ru^(II) or Fe^(II) centers are connected via π-conjugated bridges to six electron-accepting N-methyl-/N-arylpyridinium groups. This work builds upon our previous preliminary studies (Coe, B. J. J. Am. Chem. Soc. 2005, 127, 13399-13410; J. Phys. Chem. A 2007, 111, 472-478), with the aims of achieving greatly enhanced NLO properties and also combining large quadratic and cubic effects in potentially redox-switchable molecules. Characterization has involved various techniques, including electronic absorption spectroscopy and cyclic voltammetry. The complexes display intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) bands, and their π → π^* intraligand charge-transfer (ILCT) absorptions in the near-UV region show molar extinction coefficients as high as ca. 3.5 × 10^5 M^(-1) cm^(-1). Molecular quadratic nonlinear optical (NLO) responses β have been determined by using hyper-Rayleigh scattering at 800 and 1064 nm and also via Stark (electroabsorption) spectroscopic studies. The directly and indirectly derived β values are very large, with the Stark-based static first hyperpolarizabilities β_0 reaching as high as ca. 10^(-27) esu, and generally increase on extending the π-conjugation and enhancing the electron-accepting strength of the ligands. Cubic NLO properties have also been measured by using the Z-scan technique, revealing relatively high two-photon absorption cross sections of up to 2500 GM at 750 nm.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja910538sDOIArticle
http://pubs.acs.org/doi/full/10.1021/ja910538sPublisherArticle
ORCID:
AuthorORCID
Coe, Benjamin J.0000-0002-5998-3895
Fielden, John0000-0001-5963-7792
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2010 American Chemical Society. Published In Issue March 17, 2010. Article ASAP February 18, 2010. Received: December 14, 2009. We thank the EPSRC for support (grants EP/D070732 and EP/E000738) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), the NSF (grant CHE-0802907, ‘Powering the Planet: an NSF Center for Chemical Innovation’) and the Foundation for Polish Science. I.A. is a postdoctoral fellow of the FWO-V and M.S. is a Laureate of the FNP Welcome programme.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/D070732
Engineering and Physical Sciences Research Council (EPSRC)EP/E000738
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)G.0312.08
University of LeuvenGOA/2006/3
NSFCHE-0802907
Foundation for Polish ScienceUNSPECIFIED
Issue or Number:10
Record Number:CaltechAUTHORS:20100408-153120348
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20100408-153120348
Official Citation:Combining Very Large Quadratic and Cubic Nonlinear Optical Responses in Extended, Tris-Chelate Metallochromophores with Six π-Conjugated Pyridinium Substituents Benjamin J. Coe, John Fielden, Simon P. Foxon, Bruce S. Brunschwig, Inge Asselberghs, Koen Clays, Anna Samoc, Marek Samoc Journal of the American Chemical Society 2010 132 (10), 3496-3513
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:17910
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:09 Apr 2010 21:24
Last Modified:03 Oct 2019 01:35

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