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The syntheses, structures and nonlinear optical and related properties of salts with julolidinyl electron donor groups

Coe, Benjamin J. and Foxon, Simon P. and Harper, Elizabeth C. and Harris, James A. and Helliwell, Madeleine and Raftery, James and Asselberghs, Inge and Clays, Koen and Franz, Edith and Brunschwig, Bruce S. and Fitch, Anthony G. (2009) The syntheses, structures and nonlinear optical and related properties of salts with julolidinyl electron donor groups. Dyes and Pigments, 82 (2). pp. 171-186. ISSN 0143-7208.

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Twelve, dipolar cations with 2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl (julolidinyl, Jd) electron donor groups and N-methyl/arylpyridinium, N-methylquinolinium or N-methylbenzothiazolium acceptor groups were synthesised. The chromophores were characterised as their PF^-_6 salts using various techniques including electronic absorption spectroscopy and cyclic voltammetry; single crystal X-ray structures were determined for a large number of salts, all of which form nonpolar materials. A broad correlation between the electron acceptor strength and the degree of bond length alternation is evident. A key focus of this work is detailed comparisons of the Jd-containing chromophores with their previously studied 4-(dimethylamino)phenyl (Dap) analogues. Molecular, quadratic, nonlinear optical responses were determined using femtosecond hyper-Rayleigh scattering at both 1300 and 800 nm, as well as using Stark (electroabsorption) spectroscopic studies of intense, visible π → π* intramolecular charge-transfer bands. Substantial red shifts in the latter transitions are observed on replacing Dap with Jd which indicate that the latter acts as a more effective π-electron donor. With few exceptions, both hyper-Rayleigh scattering and Stark data generally show that using Jd instead of Dap increases the static first hyperpolarizability β_0, in accord with expectations based on the two-state model. β_0 values as high as 6 times larger than that of the chromophore in the technologically important material E-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate are observed.

Item Type:Article
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URLURL TypeDescription
Coe, Benjamin J.0000-0002-5998-3895
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2009 Elsevier. Received 21 October 2008; revised 22 December 2008; accepted 23 December 2008. Available online 3 January 2009. We thank the EPSRC for support (grants GR/M93864 and EP/D070732 and a PhD studentship to ECH) and also the Fund for Scientific Research-Flanders (FWO-V, G.0312.08) and the University of Leuven (GOA/2006/3).We thank Dr. John E.Warren (Synchrotron Radiation Source, CCLRC, Daresbury Laboratory, Warrington, WA4 4AD, UK) for assistance with the crystal structure determination of compound [10]BPh_4.
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)GR/M93864
Engineering and Physical Sciences Research Council (EPSRC)EP/D070732
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)G.0312.08
University of LeuvenGOA/2006/3
Subject Keywords:Organic synthesis; Nonlinear optics; Julolidinyl dyes; Hyper-Rayleigh scattering; Stark spectroscopy
Issue or Number:2
Record Number:CaltechAUTHORS:20090814-141122835
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15050
Deposited By: Tony Diaz
Deposited On:17 Aug 2009 16:37
Last Modified:03 Oct 2019 00:54

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