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Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores

Coe, Benjamin J. and Foxon, Simon P. and Harper, Elizabeth C. and Helliwell, Madeleine and Raftery, James and Swanson, Catherine A. and Brunschwig, Bruce S. and Clays, Koen and Franz, Edith and Garin, Javier and Orduna, Jesús and Horton, Peter N. and Hursthouse, Michael B. (2010) Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores. Journal of the American Chemical Society, 132 (5). pp. 1706-1723. ISSN 0002-7863.

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In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845−4859). They have been isolated as their PF_6− salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant β_0 responses as high as ca. 600 × 10^(−30) esu. These pseudo-C_(2v) chromophores show two substantial components of the β tensor, β_(zzz) and β_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, β_(zzz) dominates in all cases, whereas the Stark analyses indicate that β_(zyy) is dominant in the shorter chromophores, but β_(zzz) and β_(zyy) are similar for the extended species. In contrast, finite field calculations predict that β_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand π-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880−3891).

Item Type:Article
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Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2010 American Chemical Society. Received October 20, 2009. Publication Date (Web): January 15, 2010. We thank the EPSRC for support (grant EP/D070732/1) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), MCyT-FEDER (CTQ2005-01368, CTQ2008-02942), the NSF (grant CHE-0802907, “Powering the Planet: an NSF Center for Chemical Innovation”) and Gobierno de Aragon-Fondo Social Europeo (E39). We are grateful to Dr. Inge Asselberghs for technical assistance with the analysis of the HRS data.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/D070732/1
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)G.0312.08
University of LeuvenGOA/2006/3
Ministerio de Ciencia y Tecnología (MCyT)CTQ2005-01368
Ministerio de Ciencia y Tecnología (MCyT)CTQ2008-02942
Gobierno de Aragon-Fondo Social EuropeoE39
Fondo Europeo de Desarrollo Regional (FEDER)UNSPECIFIED
Issue or Number:5
Record Number:CaltechAUTHORS:20100401-105537118
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Official Citation:Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores Benjamin J. Coe, Simon P. Foxon, Elizabeth C. Harper, Madeleine Helliwell, James Raftery, Catherine A. Swanson, Bruce S. Brunschwig, Koen Clays, Edith Franz, Javier Garn, Jess Orduna, Peter N. Horton, Michael B. Hursthouse Journal of the American Chemical Society 2010 132 (5), 1706-1723
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:17838
Deposited By: Ruth Sustaita
Deposited On:06 Apr 2010 21:03
Last Modified:03 Oct 2019 01:34

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