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Syntheses and Properties of Salts of Chromophores with Ferrocenyl Electron Donor Groups and Quaternary Nitrogen Acceptors

Coe, Benjamin J. and Docherty, Rebecca J. and Foxon, Simon P. and Harper, Elizabeth C. and Helliwell, Madeleine and Raftery, James and Clays, Koen and Franz, Edith and Brunschwig, Bruce S. (2009) Syntheses and Properties of Salts of Chromophores with Ferrocenyl Electron Donor Groups and Quaternary Nitrogen Acceptors. Organometallics, 28 (24). pp. 6880-6892. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20100114-133116831

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Abstract

A series of five new dipolar cations has been synthesized with ferrocenyl (Fc) electron donor groups connected to N-arylpyridinium, N-methylquinolinium, N-methylbenzothiazolium, or N-methylacridinium acceptors. Together with their known N-methylpyridinium analogue, these chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Nine single-crystal X-ray structures have been determined, including two polymorphs of one salt obtained from a single crystallization experiment, and two of these are polar materials. A highly favorable degree of dipolar alignment for bulk NLO effects is observed in one case. Molecular quadratic nonlinear optical (NLO) responses have been determined by using femtosecond hyper-Rayleigh scattering (HRS) at 1300 nm and also via Stark (electroabsorption) spectroscopic studies on the intense π → π^* intraligand and d → π^* metal-to-ligand charge-transfer bands. A broad correlation between the electron acceptor strength and the HRS-derived first hyperpolarizabilities β and the static first hyperpolarizabilities β0 estimated from the Stark data is evident. This is the first time that meaningful (albeit indirectly determined) β_0 data have been reported for Fc compounds, allowing quantitative comparisons with the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium (DAS) tosylate. The observed β_0 values are in several cases similar to that of [DAS]PF_6, and possibly even larger in one instance.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om9007955DOIArticle
http://pubs.acs.org/doi/abs/10.1021/om9007955PublisherArticle
ORCID:
AuthorORCID
Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2009 American Chemical Society. Received September 11, 2009. Publication Date (Web): November 12, 2009. We thank the EPSRC for support in the form of a Ph.D. studentship (E.C.H.) and a postdoctoral grant (S.P.F., EP/D070732), and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08) and the University of Leuven (GOA/2006/3). B.S.B. acknowledges support from the NSF (CHE-0802907, ‘Powering the Planet: an NSF Center for Chemical Innovation’).
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/D070732
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)G.0312.08
University of LeuvenGOA/2006/3
NSFCHE-0802907
Issue or Number:24
Record Number:CaltechAUTHORS:20100114-133116831
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20100114-133116831
Official Citation:Syntheses and Properties of Salts of Chromophores with Ferrocenyl Electron Donor Groups and Quaternary Nitrogen Acceptors Benjamin J. Coe, Rebecca J. Docherty, Simon P. Foxon, Elizabeth C. Harper, Madeleine Helliwell, James Raftery, Koen Clays, Edith Franz, Bruce S. Brunschwig Organometallics 2009 28 (24), 6880-6892
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:17186
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:21 Jan 2010 19:27
Last Modified:03 Oct 2019 01:24

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