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Syntheses and quadratic nonlinear optical properties of salts containing benzothiazolium electron-acceptor groups

Coe, B.J., Harris, J.A., Hall, J.J., Brunschwig, B.S., Hung, S.T., Libaers, W., Clays, K., Coles, S.J., Horton, P.N., Light, M.E., Hursthouse, M.B., Garin, J. and Orduna, J. (2006) Syntheses and quadratic nonlinear optical properties of salts containing benzothiazolium electron-acceptor groups Chemistry of Materials, 18, (25), pp. 5907-5918. (doi:10.1021/cm061594t).

Record type: Article

Abstract

A series of chromophoric salts has been prepared in which electron-rich 4-(dimethylamino) phenyl groups are connected via polyenyl chains to electron-accepting N-methylpyridinium or 3-methylbenzothiazolium units. These compounds have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Single-crystal X-ray structures have been determined for several salts, all of which crystallize centrosymmetrically. Molecular quadratic nonlinear optical (NLO) responses have been determined using femtosecond hyper-Rayleigh scattering (HRS) at 1300 and 800 nm and via Stark (electroabsorption) spectroscopic studies on the intense, visible pi ->pi* intramolecular charge-transfer (ICT) bands. Large red shifts in the ICT transitions on replacing a pyridinium with a benzothiazolium unit indicate that the latter acts as a more effective electron acceptor. Both HRS and Stark measurements show that the static first hyperpolarizability, beta(0) increases with polyene chain extension in both types of chromophore, and the benzothiazolium salts have larger NLO responses than their pyridinium analogues. The results of time-dependent density functional theory calculations using a polarizable solvent continuum model agree with the observation that, beta(0) increases with chain lengthening, but the observed superiority of the benzothiazolium acceptor is not predicted either in the ICT energies or, beta(0) values. Coupled perturbed Hartree-Fock and semiempirical INDO/S calculations similarly fail to reproduce this principal conclusion from the experimental studies.

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Published date: 2006

Identifiers

Local EPrints ID: 44408
URI: http://eprints.soton.ac.uk/id/eprint/44408
ISSN: 0897-4756
PURE UUID: 5c8edb20-a9ad-434c-bb75-6dda3cc2c754
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for P.N. Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for M.E. Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 06 Mar 2007
Last modified: 17 Jul 2017 15:14

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Contributors

Author: B.J. Coe
Author: J.A. Harris
Author: J.J. Hall
Author: B.S. Brunschwig
Author: S.T. Hung
Author: W. Libaers
Author: K. Clays
Author: S.J. Coles ORCID iD
Author: P.N. Horton ORCID iD
Author: M.E. Light ORCID iD
Author: M.B. Hursthouse
Author: J. Garin
Author: J. Orduna

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