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; Seth R. Marder

doi:10.1039/C2JM15599K

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

Yulia A. Getmanenko,^a Joel M. Hales,^b Mihaela Balu,^b Jie Fu,^b Egbert Zojer,^ac Ohyun Kwon,^a Jeffrey Mendez,^d S. Thayumanavan,^d Gregory Walker,^e Qing Zhang,^a Scott D. Bunge,^f Jean-Luc Brédas,^a David J. Hagan,^b Eric W. Van Stryland,^b Stephen Barlow^ae and Seth R. Marder^ade

Author affiliations

^a School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA, USA

^b CREOL & FPCE, The College of Optics and Photonics and Department of Physics, University of Central Florida, Orlando, FL

^c Institute of Solid State Physics, Graz University of Technology, Graz, Austria

^d Beckman Institute, California Institute of Technology, Pasadena, USA

^e Department of Chemistry, University of Arizona, Tucson, AZ, USA

^f Department of Chemistry and Biochemistry, Kent State University, Kent, OH, USA

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 [triple bond, length as m-dash] 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 ca. 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 ca. 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.

This article is part of the themed collection: Organic optoelectronic materials

Journal of Materials Chemistry

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

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

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