Reversible luminescence thermochromism and phase transition in crystals of thiophenylacetylacetonatoboron difluoride

Мирочник, А. Г.; Федоренко, Е. В.; Kaidalova, T. A.; Merkulov, E. B.; Kuryavyi, V. G.; Galkin, K. N.; Карасев, В. Е.

doi:10.1016/j.jlumin.2008.04.016

Cited by 18 publications

(6 citation statements)

References 20 publications

(22 reference statements)

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“…Absorption peaks are observed at 380 and 410 nm. The band at 380 nm is assigned to the π-π* transition of the electron density delocalized over the whole molecule, as reported by Mirochnik et al 32,33 The absorbance is not proportional to the concentration of the dye, suggesting that there are intermolecular interactions between the BF 2 AVB molecules in polymer films. The absorption spectra are flat around the peak for BF 2 AVB concentrations up to 0.7 mol%.…”

Section: Methodssupporting

confidence: 56%

Concentration-Dependent Fluorescence Color Tuning of the Difluoroboron Avobenzone Complex in Polymer Films

Ito¹,

Kikuchi²

2017

Bulletin of the Chemical Society of Japan

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We have investigated concentration-dependent fluorescence color tuning of BF 2 AVB in a poly(methyl methacrylate) film. BF 2 AVB exhibits a color change from purple-blue to orange via green, and then crystals segregate from the polymer matrix. We analyzed the fluorescence and fluorescence excitation spectral change as a function of the BF 2 AVB concentration in the film. We also obtained fluorescence microscope images to confirm the miscibility and crystallization properties in the films. This originates from the aggregated state formed in the polymer matrix depending on the stacking structure of the parallel (B-phase), antiparallel (G-phase), and amorphous states. The emissive species change with increasing BF 2 AVB concentration. The polymer matrix isolation method enables not only directly visualization of the dynamics of the crystal formation process and Ostwald's rule of stages by fluorescence changes, but it also enables device fabrication, such as fabrication of organic light-emitting diodes and luminescent solar concentrators.

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Section: Methodssupporting

confidence: 56%

Concentration-Dependent Fluorescence Color Tuning of the Difluoroboron Avobenzone Complex in Polymer Films

Ito¹,

Kikuchi²

2017

Bulletin of the Chemical Society of Japan

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“…The dibenzoylmethanatoboron difluoride (BF 2 DBM) derivative exhibits mechanofluorochromism in response to perturbation by a mechanical force. [10][11][12][13][14][15][16][17] BF 2 DBM derivatives are known for their impressive optical properties, such as their two-photon absorption cross-sections, 18,19 high fluorescence quantum yield even in the solid state, 20 and multi-fluorescence colors. 12,[21][22][23] Fraser et al reported a reversible mechanofluoro-chromic organic solid based on the 4-tert-butyl-4′-methoxydibenzoylmethane (trade name: avobenzone) boron difluoride complex, which exhibits different emission depending on the crystal types.…”

Section: Introductionmentioning

confidence: 99%

Substituent-dependent backward reaction in mechanofluorochromism of dibenzoylmethanatoboron difluoride derivatives

Sagawa

Ito

Sakai

et al. 2016

Photochem Photobiol Sci

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The thermally backward reaction involved in the mechanofluorochromism of dibenzoylmethanatoboron difluoride (BF2DBM) derivatives, accompanied by an amorphous-crystalline phase transition, was quantitatively evaluated based on kinetics and thermodynamics. The kinetics was discussed by evaluation of the effect of temperature on the time-dependent changes of the fluorescence intensity for amorphous samples obtained by mechanical grinding. The thermodynamics was discussed based on data for the amorphous-crystalline phase transition obtained by differential scanning calorimetry. The enthalpy of activation (ΔH(‡)) of BF2DBM derivatives with MeO groups (2aBF2) was larger than that of derivatives with alkyl groups (2b-dBF2), whereas the entropy of activation (ΔS(‡)) was smaller than that of the derivatives with alkyl groups. It is proposed that the reaction dynamics of 2aBF2 will be governed by rotational motion around the C(methyl)-O bond. Interestingly, the Gibbs energies of activation (ΔG(‡)) were comparable for the reactions of all members of the BF2DBM series, though ΔH(‡) and ΔS(‡) were strongly dependent on the identity of the substituent. It is proposed that the substituent-dependent ΔS(‡) term is one of the key parameters for understanding the mechanofluorochromism of BF2DBM derivatives associated with the amorphous-crystalline phase transition. These findings will also provide important insights into the process of formation of crystal nuclei in moving from the melted to the crystalline state.

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“…The b-diketonate boron diuoride complex exhibits a uorescence spectral change by mechanical perturbation depending on its concentration. [8][9][10][11] Fraser et al reported a reversible mechanochromic uorescent organic solid based on the 4-tertbutyl-4 0 -methoxydibenzoylmethane (trade name: avobenzone) boron diuoride complex, which shows different emission depending on the crystal type. 12 The emission color signicantly red-shis upon rubbing/smearing the samples.…”

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confidence: 99%

Quantitative evaluation of thermodynamic parameters for thermal back-reaction after mechanically induced fluorescence change

Ito

Sagawa

2013

RSC Adv.

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Kinetics of the thermal back-reaction of β-diketonate boron difluoride complexes after mechanical perturbation were evaluated by fluorescence intensity changes for the first time, suggesting that the activation parameters of the reaction intermediates governed intermolecular interactions such as 10 hydrogen bonding assisted by substituent groups. we studied and quantitatively evaluated for the first time the thermodynamic parameters for thermal back-reaction after mechanically induced fluorescence change. The molecular structure of boron difluoride β-diketonate complexes is shown in Chart 1. In this study we used 1-(4-tert-55 butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione (ab), 1,3-bis-(4-methoxyphenyl)-1,3-propanedione (2a), and 1,3-bis-(4-tert-butylphenyl)-1,3-propanedione (2b) as ligands. The boronation was performed by BF 3 ·OEt 2 in CH 2 Cl 2 according to a previous report. 12 The purification was carried out with column 60 chromatography. A 2.0×10 -3 mol·dm -3 dichloromethane solution was dropped on paraffin-coated weighing paper, and then the solvent-evaporated sample was used for spectroscopic studies. Fluorescence spectra were recorded on a Shimadzu RF-5300PC fluorescence spectrophotometer. In order to apply a mechanical 65 perturbation to the boron difluoride β-diketonate complexes, the samples were rubbed with a spatula. The temperature around the sample was controlled by a home-made system using a rubber heater (Hakko) and digital temperature controller (Omron E5CN-QT).

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Reversible luminescence thermochromism and phase transition in crystals of thiophenylacetylacetonatoboron difluoride

Cited by 18 publications

References 20 publications

Concentration-Dependent Fluorescence Color Tuning of the Difluoroboron Avobenzone Complex in Polymer Films

Concentration-Dependent Fluorescence Color Tuning of the Difluoroboron Avobenzone Complex in Polymer Films

Substituent-dependent backward reaction in mechanofluorochromism of dibenzoylmethanatoboron difluoride derivatives

Quantitative evaluation of thermodynamic parameters for thermal back-reaction after mechanically induced fluorescence change

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