Remarkably Slow Aggregation of a Styrylpyrazine Amphiphile in Aqueous Dispersion

Park, Jong-Mok; Zhang, Wanbin; Nakatsuji, Yohji; Majima, Tetsuro; Ikeda, Isao

doi:10.1246/cl.2000.182

Cited by 5 publications

(3 citation statements)

References 14 publications

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“…Variable-concentration TMC-2 and TMC-3 fluorescence spectra in CH 2 Cl 2 provide further evidence of TMC aggregation. The unexpected blue shift of the TMC-2 fluorescence spectra for the H-type aggregates could conceivably be due to unusually slow radiationless relaxation between exciton-split states, resulting in TMC-2 fluorescence from the higher energy state . An alternative explanation for the inverse trend observed in the TMC-2 fluorescence spectra invokes strong reabsorption .…”

Section: Discussionmentioning

confidence: 94%

“…The unexpected blue shift of the TMC-2 fluorescence spectra for the H-type aggregates could conceivably be due to unusually slow radiationless relaxation between exciton-split states, resulting in TMC-2 fluorescence from the higher energy state. 65 An alternative explanation for the inverse trend observed in the TMC-2 fluorescence spectra invokes strong reabsorption. 66 In contrast, the TMC-3 dimers exhibit more conventional red-shifted florescence.…”

Section: Tictoid Chromophore Synthetic Strategies and Stabilitymentioning

confidence: 99%

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Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores: Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies

Kang¹,

Facchetti²,

Jiang³

et al. 2007

J. Am. Chem. Soc.

272

197

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This contribution details the synthesis and chemical/physical characterization of a series of unconventional twisted pi-electron system electro-optic (EO) chromophores. Crystallographic analysis of these chromophores reveals large ring-ring dihedral twist angles (80-89 degrees) and a highly charge-separated zwitterionic structure dominating the ground state. NOE NMR measurements of the twist angle in solution confirm that the solid-state twisting persists essentially unchanged in solution. Optical, IR, and NMR spectroscopic studies in both the solution phase and solid state further substantiate that the solid-state structural characteristics persist in solution. The aggregation of these highly polar zwitterions is investigated using several experimental techniques, including concentration-dependent optical and fluorescence spectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopy in combination with solid-state data. These studies reveal clear evidence of the formation of centrosymmetric aggregates in concentrated solutions and in the solid state and provide quantitative information on the extent of aggregation. Solution-phase DC electric-field-induced second-harmonic generation (EFISH) measurements reveal unprecedented hyperpolarizabilities (nonresonant mubeta as high as -488,000 x 10(-48) esu at 1907 nm). Incorporation of these chromophores into guest-host poled polyvinylphenol films provides very large electro-optic coefficients (r(33)) of approximately 330 pm/V at 1310 nm. The aggregation and structure-property effects on the observed linear/nonlinear optical properties are discussed. High-level computations based on state-averaged complete active space self-consistent field (SA-CASSCF) methods provide a new rationale for these exceptional hyperpolarizabilities and demonstrate significant solvation effects on hyperpolarizabilities, in good agreement with experiment. As such, this work suggests new paradigms for molecular hyperpolarizabilities and electro-optics.

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Section: Discussionmentioning

confidence: 94%

Section: Tictoid Chromophore Synthetic Strategies and Stabilitymentioning

confidence: 99%

Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores: Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies

Kang¹,

Facchetti²,

Jiang³

et al. 2007

J. Am. Chem. Soc.

272

197

View full text Add to dashboard Cite

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“…Supramolecular assemblies responding to external stimulus such as light and gas have drawn much attention due to their potential applications in the fields of photoelectron devices, photoswitching, optical data recording, and gas or photosensor systems. − To date, photochemical reactions have been widely investigated in various organized systems such as Langmuir film, − Langmuir−Blodgett (LB) film, − self-assembly films, − bilayer membranes or vesicles, − and micelles . Monolayer and Langmuir−Blodgett methods are among the most effective ways in controlling the molecular orientation and packing at the molecular level and are some of the powerful methods to fabricate functional ultrathin films .…”

Section: Introductionmentioning

confidence: 99%

Photochemical Reaction, Acidichromism, and Supramolecular Nanoarchitectures in the Langmuir−Blodgett Films of an Amphiphilic Styrylquinoxaline Derivative

et al. 2004

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An amphiphilic styrylquinoxaline derivative, 3-(4-(hexadecyloxy)styryl)quinoxalin-2(1H)-one (SQC16), was newly synthesized to investigate their photochemical and gas responsive properties in organized molecular films. It was observed that SQC16 can spread as a monolayer on the subphases with various pH values and be subsequently transferred onto solid substrates. While SQC16 showed predominantly reversible trans-cis photoisomerization in methanol solution, it showed both photoisomerization and photodimerization in Langmuir-Blodgett (LB) films. Photodimerization was only observed in the LB film due to the face-to-face arrangement of the functional headgroup in the LB film, and the process was irreversible. In addition, the LB film showed acidichromism, i.e., when the film was exposed to HCl gas its color changed from yellow to red, and the color could be recovered after exposure to NH(3) gas. The process was reversible and could be repeated many times. An interesting surface morphology of the SQC16 LB film was revealed. It was observed that SQC16 can form nanowire architecture in the transferred one-layer LB film. This morphology can be changed upon photoirradiation or in gas reactions. Through the atomic force microscopy measurements it was suggested that the photodimerization predominantly occurred from the nanowire structures, while during the acidichromism the reaction occurred preferentially in the flat region. X-ray diffraction studies revealed that while layer distance showed a slight change for the LB film during acidichromism and photoreaction, the layer structure of SQC16 LB film was retained.

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Ionic liquids based on (fluorosulfonyl)(pentafluoroethanesulfonyl)imide with various oniums

Zhou

Han

et al. 2010

Electrochimica Acta

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Remarkably Slow Aggregation of a Styrylpyrazine Amphiphile in Aqueous Dispersion

Cited by 5 publications

References 14 publications

Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores: Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies

Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores: Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies

Photochemical Reaction, Acidichromism, and Supramolecular Nanoarchitectures in the Langmuir−Blodgett Films of an Amphiphilic Styrylquinoxaline Derivative

Ionic liquids based on (fluorosulfonyl)(pentafluoroethanesulfonyl)imide with various oniums

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