Synthesis and linear and nonlinear optical properties of metal-terminated bis(dioxaborine) polymethines

Lin, Hsin‐Chieh; Kim, Hyeongeu; Barlow, Stephen; Hales, Joel M.; Perry, Joseph W.; Marder, Seth R.

doi:10.1039/c0cc02003f

Cited by 26 publications

(14 citation statements)

References 21 publications

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“…One way to solve this problem is to modify the charge‐stabilizing end groups of cyanines to enable more efficient delocalization of the π‐electrons throughout the whole molecule, while still keeping L < C9 . For example, a heptamethine based on the selenopyrylium end group shows a very large Re( γ ) of

- 2.2 \times 10^{- 31}

esu with a high molecular FOM, above 100 in dilute solutions .…”

Section: Methodsmentioning

confidence: 99%

Conjugated Polycyanines: A New Class of Materials with Large Third‐Order Optical Nonlinearities

Ensley

et al. 2015

Advanced Optical Materials

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A fully conjugated polycyanine (AJMPC02) showing a very large Re(γ) value of −9.0 × 10−57 mks at 1.3 μm is synthesized. It is used as a host polymer for anionic TCF‐cyanines for creating a complementary polymeric cyanine salt complex, which exhibits a Re(γ) value of −5.6 × 10−57 mks at 1.3 μm. A good optical quality thin film based on AJMPC02‐TCF gives a Re(γ) value of −2.1 × 10−18 mks at 1.3 μm and −8.5 × 10−19 mks at 1.55 μm, which are among the highest values reported for molecular materials, and much higher than those derived from silicon.

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- 2.2 \times 10^{- 31}

esu with a high molecular FOM, above 100 in dilute solutions .…”

Section: Methodsmentioning

confidence: 99%

Conjugated Polycyanines: A New Class of Materials with Large Third‐Order Optical Nonlinearities

Ensley

et al. 2015

Advanced Optical Materials

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“…Difluoroboron β‐diketonate complexes, 2,2‐difluoro‐1,3,2‐dioxaborines, are highly luminescent organoboron compounds with many appealing attributes such as large extinction coefficients, bright fluorescence in both solution and the solid state, tunable fluorescent emission, and two‐photon excited fluorescence . Polymethine dyes based on dioxaborines are intensely colored fluorophores widely used in nonlinear optical (NLO) materials, as fluorescence probes for serum albumins, labels for proteins and DNA, and as fluorescent molecular rotors …”

Section: Introductionmentioning

confidence: 99%

D–π–A–π–D Dyes with a 1,3,2‐Dioxaborine Cycle in the Polymethine Chain: Efficient Long‐Wavelength Fluorophores

et al. 2018

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The nitrile group in newly synthesized 5‐cyano‐2,2‐difluoro‐4,6‐dimethyl‐1,3,2‐dioxaborine is shown to significantly increase the acidity of the methyl groups. This allows the cyanine condensation with both methyl groups to form D–π–A–π–D dyes in which the dioxaborine cycle is a part of the polymethine chain. There, the reactivity of the remaining methyl group in the semi‐product is reduced enough to perform the reaction stepwise, giving access to nonsymmetric derivatives. The synthesis of dyes with various electron donor termini [indole, benzothiazole, pyran, 4‐(dialkylamino)phenyl] and with different polymethine chain lengths is reported. The obtained compounds show intense absorption and fluorescence in the red and NIR region, their fluorescence brightness (the product of the molar extinction and the fluorescence quantum yield) attaining a value of 200,000 m–1 cm–1. They are characterized by small‐scale positive solvatochromism, yet their fluorescence quantum yield is much more sensitive to ambient polarity. Time‐dependent (TD)DFT calculations have been performed to study the electronic structure of the new dioxaborines and reveal the nature of the long‐wavelength electronic transitions in those molecules.

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“…Additionally, conversion from the macroscopic nonlinear optical parameters extracted from Z-scan measurements and the microscopic parameters discussed herein are given in ref. 90.…”

Section: Nonlinear Optical Characterisationmentioning

confidence: 99%

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

et al. 2012

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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 mm 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 p-p 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 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 crosssections. 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.

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Synthesis and linear and nonlinear optical properties of metal-terminated bis(dioxaborine) polymethines

Cited by 26 publications

References 21 publications

Conjugated Polycyanines: A New Class of Materials with Large Third‐Order Optical Nonlinearities

Conjugated Polycyanines: A New Class of Materials with Large Third‐Order Optical Nonlinearities

D–π–A–π–D Dyes with a 1,3,2‐Dioxaborine Cycle in the Polymethine Chain: Efficient Long‐Wavelength Fluorophores

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

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