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Contrasting Linear and Quadratic Nonlinear Optical Behavior of Dipolar Pyridinium Chromophores with 4-(Dimethylamino)phenyl or Ruthenium(II) Ammine Electron Donor Groups

Coe, Benjamin J. and Harris, James A. and Brunschwig, Bruce S. and Garín, Javier and Orduna, Jesús and Coles, Simon J. and Hursthouse, Michael B. (2004) Contrasting Linear and Quadratic Nonlinear Optical Behavior of Dipolar Pyridinium Chromophores with 4-(Dimethylamino)phenyl or Ruthenium(II) Ammine Electron Donor Groups. Journal of the American Chemical Society, 126 (33). pp. 10418-10427. ISSN 0002-7863. doi:10.1021/ja047650d. https://resolver.caltech.edu/CaltechAUTHORS:20170405-143024724

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Abstract

In this article, we contrast the optical properties of dipolar chromophores having 4-(dimethylamino)phenyl electron donor (D) and pyridinium acceptor (A) groups with those of closely related cations having pyridyl-coordinated RuII donors. A range of physical data, including that from Stark (electroabsorption) spectroscopy, permits unprecedented quantitative comparisons, most notably regarding the effects of extension of bridging polyene chains. The purely organic compounds display normal optical properties in that their intense, visible π → π* intramolecular charge-transfer (ICT) bands red-shift as the number of E-ethylene units (n) increases from 1 to 3 and the associated static first hyperpolarizabilities β_0 increase steadily with n. The related RuII complexes show intense, visible d → π* metal-to-ligand charge-transfer (MLCT) bands, which are found to lower energy when compared with the ICT transitions of the corresponding organics. Abnormally, these MLCT bands blue-shift as n increases, and β_0 maximizes at n = 2. Time-dependent density-functional theory and finite field calculations verify these empirical trends for both types of compound, which can be rationalized as arising from the differing orbital structures of the chromophores and the associated degrees of D−A electronic coupling.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja047650dDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja047650dPublisherArticle
ORCID:
AuthorORCID
Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2004 American Chemical Society. Received April 23, 2004, Publication Date (Web): August 3, 2004. We thank the EPSRC for support (a studentship and Grants GR/M93864 and GR/R54293) and also 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
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:33
DOI:10.1021/ja047650d
Record Number:CaltechAUTHORS:20170405-143024724
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170405-143024724
Official Citation:Contrasting Linear and Quadratic Nonlinear Optical Behavior of Dipolar Pyridinium Chromophores with 4-(Dimethylamino)phenyl or Ruthenium(II) Ammine Electron Donor Groups Benjamin J. Coe, James A. Harris, Bruce S. Brunschwig, Javier Garín, Jesús Orduna, Simon J. Coles, and Michael B. Hursthouse Journal of the American Chemical Society 2004 126 (33), 10418-10427 DOI: 10.1021/ja047650d
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75742
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:05 Apr 2017 21:40
Last Modified:15 Nov 2021 16:36

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