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Cross-conjugation as a Motif for Organic Non-Linear Optical Molecules

Published online by Cambridge University Press:  19 August 2014

Meghana Rawal ,
Kerry Garrett ,
Andreas F. Tillack ,
Werner Kaminsky ,
Evgheni Jucov ,
David P. Shelton ,
Tatiana V. Timofeeva ,
Bruce E. Eichinger ,
Bruce H. Robinson  and
Larry R. Dalton
Meghana Rawal
Affiliation:
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, U.S.A.
Kerry Garrett
Affiliation:
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, U.S.A.
Andreas F. Tillack
Affiliation:
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, U.S.A.
Werner Kaminsky
Affiliation:
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, U.S.A.
Evgheni Jucov
Affiliation:
Department of Chemistry, New Mexico Highlands University, Las Vegas, NM 87701, U.S.A.
David P. Shelton
Affiliation:
Department of Physics, University of Nevada, Las Vegas, NV 89154, U.S.A.
Tatiana V. Timofeeva
Affiliation:
Department of Chemistry, New Mexico Highlands University, Las Vegas, NM 87701, U.S.A.
Bruce E. Eichinger
Affiliation:
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, U.S.A.
Bruce H. Robinson
Affiliation:
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, U.S.A.
Larry R. Dalton
Affiliation:
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195, U.S.A.
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Abstract

We studied the effect of a cross-conjugated bridging group (χC) on charge-transfer in a push-pull chromophore system. The hyperpolarizability of such molecules was found to be comparable to that of a fully π-conjugated molecule (πC) with the same donor and acceptor. The cross-conjugated moiety was then applied as a pendant to a fully π-conjugated chromophore containing a tricyanopyrroline acceptor (TCP). The addition of a χC moiety did not alter the intrinsic hyperpolarizability and provides an avenue for extending and aiding πC systems. The molecules were examined by X-ray diffraction (XRD), hyper-Raleigh scattering (HRS) and UV-visible (UV-vis) spectroscopy. Experimental results were compared with the predictions of density functional theory (DFT). Cross-conjugated molecules have comparable β values, relative to πC molecules, due to reduced spatial overlap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). Thus, the χC architecture could facilitate independent modification of donor and acceptor strengths while minimizing unfavorable effects on electronic transitions and dipole moments.

Keywords

electronic materialchemical synthesiselectronic structure
Type
Articles
Information
MRS Online Proceedings Library (OPL) , Volume 1698: Symposium II/JJ/KK – Materials, Processes and Devices for Nanophotonics, Nonlinear Optics and Resonant Optics , 2014 , mrss14-1698-jj01-01
Copyright
Copyright © Materials Research Society 2014 

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References

REFERENCES

van der Veen, M.H., et al. ., Adv. Funct. Mater. 14, 215 (2004).CrossRefGoogle Scholar
Almenningen, A. et al. ., Acta Chem. Scand. 42A, 634 (1988).Google Scholar
Swager, T.M. and Grubbs, R.H., J. Am. Chem. Soc. 109, 894 (1987).CrossRefGoogle Scholar
Wu, P.L. et al. ., Chem. Commun. 5421 (2009).Google Scholar
Feng, X.J. et al. ., Chem. – Eur. J. 17, 2518 (2011).CrossRefGoogle Scholar
Michinobu, T. et al. ., Chem. Commun. 737 (2005).Google Scholar
May, J.C. et al. ., Opt. Lett. 30, 3057 (2005).CrossRefGoogle Scholar
Michinobu, T. et al. ., Chem. – Eur. J. 12, 1889 (2006).Google Scholar
Tykwinski, R.R. and Zhao, Y., Synlett 1939 (2002).Google Scholar
Zhao, Y. and Tykwinski, R.R., J. Am. Chem. Soc. 121, 458 (1999).CrossRefGoogle Scholar
van Walree, C.A., et al. ., Eur. J. Org. Chem. 2004, 3046 (2004).CrossRefGoogle Scholar
Solomon, G.C. et al. ., J. Am. Chem. Soc. 130, 7788 (2008).CrossRefGoogle Scholar
Kodaira, T. et al. ., J. Chem. Soc. Faraday Trans. 93, 3039 (1997).Google Scholar
Kaatz, P. and Shelton, D.P., J. Chem. Phys. 105, 3918 (1996).CrossRefGoogle Scholar
Oudar, J.L. and Chemla, D.S., J. Chem. Phys. 66, 2664 (1977).Google Scholar
Benight, S.J. et al. , J. Phys. Chem. B 114, 11949 (2010).CrossRefGoogle Scholar
Tillack, A.F. et al. ., in Mater. Res. Soc. Symp. Proc. (this issue).Google Scholar
Cho, M.J. et al. . Dyes Pigments 79, 193 (2008).Google Scholar
Bale, D.H., Ph.D. Thesis, University of Washington, 2008.Google Scholar