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Published January 10, 2012 | Supplemental Material + Published
Journal Article Open

Characterisation of a dipolar chromophore with third-harmonic generation applications in the near-IR

Abstract

E-2-Tricyanovinyl-3-n-hexyl-5-[4-{bis(4-n-butylphenyl)amino}-2-methoxystyryl]-thiophene, 1, has previously been used to demonstrate applications relying on frequency tripling of 1.55 μm light. Here we report the synthesis and chemical characterisation of 1, along with quantum-chemical calculations and additional experimental investigations of its third-order nonlinear properties that give more insight into its frequency tripling properties. Although 1 can be processed into amorphous films, crystals can also be grown by slow evaporation of solutions; the crystal structure determined by X-ray diffraction shows evidence of significant contributions from zwitterionic resonance forms to the ground-state structure, and reveals centrosymmetric packing exhibiting π–π and C–H···N≡C interactions. Both solutions and films of 1 exhibit near-infrared two-photon absorption into the low-lying one-photon-allowed state with a peak two-photon cross-section of cɑ. 290 GM (measured using the white-light continuum method with a pump wavelength of 1800 nm) at a transition energy equivalent to degenerate two-photon absorption at cɑ. 1360 nm; two related chromophores are also found to show comparable near-IR two-photon cross-sections. Closed-aperture Z-scan measurements and quantum-chemical calculations indicate that the nonlinear refractive index and third-harmonic generation properties of 1 are strongly dependent on frequency in the telecommunications range, due the aforementioned two-photon resonance.

Additional Information

© 2012 Royal Society of Chemistry. Received 1st November 2011, Accepted 1st December 2011. First published on the web 10 Jan 2012. This material is based upon work supported in part by the National Science Foundation STC Program under Agreement Number DMR-0120967 and the Defense Advanced Research Projects Agency (DARPA) MORPH Program and Office of Naval Research (N00014-04-0095 and N00014-06-1-0897). We are grateful to William Porter III and Adam Matzger (University of Michigan) for performing the polymer-induced heteronucleation experiments. We also thank Myoungsik Cha, Canek Fuentes-Hernandez, and Bernard Kippelen for fabrication of the guest-host films used in the nonlinear optical characterisation measurements.

Attached Files

Published - Getmanenko2012p17788J_Mater_Chem.pdf

Supplemental Material - c2jm15599k.pdf

Supplemental Material - c2jm15599k.txt

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Created:
August 19, 2023
Modified:
October 17, 2023