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Two-Dimensional, Pyrazine-Based Nonlinear Optical Chromophores with Ruthenium(II) Ammine Electron Donors

Coe, Benjamin J. and Fielden, John and Foxon, Simon P. and Asselberghs, Inge and Clays, Koen and Brunschwig, Bruce S. (2010) Two-Dimensional, Pyrazine-Based Nonlinear Optical Chromophores with Ruthenium(II) Ammine Electron Donors. Inorganic Chemistry, 49 (22). pp. 10718-10726. ISSN 0020-1669.

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Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru^(II)(NH_3)_5}^(2+) or trans-{Ru^(II)(NH_3)_4(py)}^(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru^(II) centers from one to two, but remain at constant energy. One or two Ru^(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant “off-diagonal” β_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities β_0. Both the HRS and the Stark-derived β_0 values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru^(II) ammine complexes reported previously.

Item Type:Article
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URLURL TypeDescription DOIArticle
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. Received September 20, 2010. Publication Date (Web): October 20, 2010. We thank the EPSRC for support (Grants EP/E000738 and EP/D070732) and also the Fund for ScientificResearch-Flanders (FWO-V, G.0312.08), the University of Leuven (GOA/2006/3), and the NSF (Grant CHE-0802907, “Powering the Planet: an NSF Center for Chemical Innovation”). I.A. is a postdoctoral fellow of the FWO-V.
Group:CCI Solar Fuels
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/E000738
Engineering and Physical Sciences Research Council (EPSRC)EP/D070732
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)G.0312.08
University of LeuvenGOA/2006/3
Issue or Number:22
Record Number:CaltechAUTHORS:20101220-094653213
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Official Citation:Two-Dimensional, Pyrazine-Based Nonlinear Optical Chromophores with Ruthenium(II) Ammine Electron Donors Benjamin J. Coe, John Fielden, Simon P. Foxon, Inge Asselberghs, Koen Clays, Bruce S. Brunschwig Inorganic Chemistry 2010 49 (22), 10718-10726
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:21428
Deposited By: Tony Diaz
Deposited On:05 Jan 2011 19:17
Last Modified:03 Oct 2019 02:24

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