A Caltech Library Service

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

Getmanenko, Yulia A. and Hales, Joel M. and Balu, Mihaela and Fu, Jie and Zojer, Egbert and Kwon, Ohyun and Mendez, Jeffrey and Thayumanavan, S. and Walker, Gregory and Zhang, Qing and Bunge, Scott D. and Brédas, Jean-Luc and Hagan, David J. and Van Stryland, Eric W. and Barlow, Stephen and Marder, Seth R. (2012) Characterisation of a dipolar chromophore with third-harmonic generation applications in the near-IR. Journal of Materials Chemistry, 22 (10). pp. 4371-4382. ISSN 0959-9428.

PDF - Published Version
See Usage Policy.

PDF - Supplemental Material
See Usage Policy.

[img] Plain Text (Crystal structure data ) - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


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.

Item Type:Article
Related URLs:
URLURL TypeDescription
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.
Funding AgencyGrant Number
NSF STC ProgramDMR-0120967
Defense Advanced Research Projects Agency (DARPA) MORPH ProgramUNSPECIFIED
Office of Naval Research (ONR)N00014-04-0095
Office of Naval Research (ONR)N00014-06-1-0897
Issue or Number:10
Record Number:CaltechAUTHORS:20120418-091816616
Persistent URL:
Official Citation:Characterisation of a dipolar chromophore with third-harmonic generation applications in the near-IR Yulia A. Getmanenko, Joel M. Hales, Mihaela Balu, Jie Fu, Egbert Zojer, Ohyun Kwon, Jeffrey Mendez, S. Thayumanavan, Gregory Walker, Qing Zhang, Scott D. Bunge, Jean-Luc Brédas, David J. Hagan, Eric W. Van Stryland, Stephen Barlow and Seth R. Marder J. Mater. Chem., 2012, 22, 4371-4382 DOI: 10.1039/C2JM15599K
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:30153
Deposited By: Ruth Sustaita
Deposited On:18 Apr 2012 16:54
Last Modified:03 Oct 2019 03:47

Repository Staff Only: item control page