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Syntheses and Spectroscopic and Quadratic Nonlinear Optical Properties of Extended Dipolar Complexes with Ruthenium(II) Ammine Electron Donor and N-Methylpyridinium Acceptor Groups

Coe, Benjamin J. and Jones, Lathe A. and Harris, James A. and Brunschwig, Bruce S. and Asselberghs, Inge and Clays, Koen and Persoons, André and Garín, Javier and Orduna, Jesús (2004) Syntheses and Spectroscopic and Quadratic Nonlinear Optical Properties of Extended Dipolar Complexes with Ruthenium(II) Ammine Electron Donor and N-Methylpyridinium Acceptor Groups. Journal of the American Chemical Society, 126 (12). pp. 3880-3891. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170420-111326547

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Abstract

In this paper, we describe the extremely unusual optical properties of RuII-based electron donor−acceptor (D−A) polyene and some closely related chromophores. For three different polyene series, the intense, visible d→π* metal-to-ligand charge-transfer bands unexpectedly blue-shift as the number of E-ethylene units (n) increases from 1 to 3, and the static first hyperpolarizabilities β0 determined via hyper-Rayleigh scattering and Stark spectroscopy maximize at n = 2, in marked contrast to other known D−A polyenes in which β_0 increases steadily with n. Time-dependent density-functional theory and finite field calculations verify these empirical trends, which arise from the orbital structures of the complexes. This study illustrates that transition metal-based nonlinear optical chromophores can show very different behavior when compared with their more thoroughly studied purely organic counterparts.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0315412DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja0315412PublisherArticle
ORCID:
AuthorORCID
Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2004 American Chemical Society. Received December 5, 2003. Publication Date (Web): March 5, 2004. We thank the EPSRC for support (Grants GR/M93864 and GR/R54293) and also the Fund for Scientific Research-Flanders (FWO-V, G.0261.02), 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.
Funders:
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)GR/M93864
Engineering and Physical Sciences Research Council (EPSRC)GR/R54293
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)G.0261.02
University of LeuvenGOA/2000/3
Belgian GovernmentIUAP P5/3
Ministerio de Ciencia y Tecnologia (MCyT)BQU2002-00219
Gobierno de Aragon-Fondo Social EuropeoP009-2001
Gobierno de Aragon-Fondo Social EuropeoE39
Department of Energy (DOE)DE-AC02-98CH10886
Fondo Europeo de Desarrollo Regional (FEDER)UNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20170420-111326547
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170420-111326547
Official Citation:Syntheses and Spectroscopic and Quadratic Nonlinear Optical Properties of Extended Dipolar Complexes with Ruthenium(II) Ammine Electron Donor and N-Methylpyridinium Acceptor Groups Benjamin J. Coe, Lathe A. Jones, James A. Harris, Bruce S. Brunschwig, Inge Asselberghs, Koen Clays, André Persoons, Javier Garín, and Jesús Orduna Journal of the American Chemical Society 2004 126 (12), 3880-3891 DOI: 10.1021/ja0315412
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76763
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:20 Apr 2017 20:39
Last Modified:03 Oct 2019 17:49

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