Crystal structures and emitting properties of trifluoromethylaminoquinoline derivatives: Thermal single-crystal-to-single-crystal transformation of polymorphic crystals that emit different colors

Yuichiro Abe, Satoru Karasawa, Noboru Koga

Research output: Contribution to journalArticle

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Abstract

2,4-Trifluoromethylquinoline (TFMAQ) derivatives that have amine (1), methylamine (2), phenylamine (3), and dimethylamine (4) substituents at the 7-position of the quinoline ring were prepared and crystallized. Six crystals including the crystal polymorphs of 2 (crystal GB and YG) and 3 (crystal B and G) were obtained and characterized by X-ray crystallography. In solution, TFMAQ derivatives emitted relatively strong fluorescence (λf max=418-469 nm and φf(s)=0.23-0.60) depending on the solvent polarity. From Lippert-Mataga plots, δμ values in the range of 7.8-14 D were obtained. In the crystalline state, TFMAQ derivatives emitted at longer wavelengths (λfmax=464-530 nm) with lower intensity (φf(c)=0.01-0.28) than those in n-hexane solution. The polymorphous crystals of 2 and 3 emitted different colors: 2, λfmax=470 and 530 nm with φf(c)=0.04 and approximately 0.01 for crystal GB and YG, respectively; and 3, λ fmax=464 and 506 nm with φf(c)=0.28 and approximately 0.28 for crystal B and G, respectively. In both crystal polymorphs of 2 and 3, crystals GB and G showed emission color changes by heating/melting/cooling cycles that were representative. By following the color changes in heating at the temperature below the melting point with X-ray diffraction measurements and X-ray crystallography, the single-crystal-to- single-crystal transformations from crystal GB to YG for 2 and from crystal B to G for 3 were revealed.

Original languageEnglish
Pages (from-to)15038-15048
Number of pages11
JournalChemistry - A European Journal
Volume18
Issue number47
DOIs
Publication statusPublished - Nov 19 2012

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Crystallization
Crystal structure
Single crystals
Color
Derivatives
Crystals
X ray crystallography
Polymorphism
Aniline Compounds
Hot Temperature
Heating
Aniline
Hexane
Amines
Melting point
Melting
Fluorescence
Crystalline materials
Cooling
X ray diffraction

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Crystal structures and emitting properties of trifluoromethylaminoquinoline derivatives : Thermal single-crystal-to-single-crystal transformation of polymorphic crystals that emit different colors. / Abe, Yuichiro; Karasawa, Satoru; Koga, Noboru.

In: Chemistry - A European Journal, Vol. 18, No. 47, 19.11.2012, p. 15038-15048.

Research output: Contribution to journalArticle

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abstract = "2,4-Trifluoromethylquinoline (TFMAQ) derivatives that have amine (1), methylamine (2), phenylamine (3), and dimethylamine (4) substituents at the 7-position of the quinoline ring were prepared and crystallized. Six crystals including the crystal polymorphs of 2 (crystal GB and YG) and 3 (crystal B and G) were obtained and characterized by X-ray crystallography. In solution, TFMAQ derivatives emitted relatively strong fluorescence (λf max=418-469 nm and φf(s)=0.23-0.60) depending on the solvent polarity. From Lippert-Mataga plots, δμ values in the range of 7.8-14 D were obtained. In the crystalline state, TFMAQ derivatives emitted at longer wavelengths (λfmax=464-530 nm) with lower intensity (φf(c)=0.01-0.28) than those in n-hexane solution. The polymorphous crystals of 2 and 3 emitted different colors: 2, λfmax=470 and 530 nm with φf(c)=0.04 and approximately 0.01 for crystal GB and YG, respectively; and 3, λ fmax=464 and 506 nm with φf(c)=0.28 and approximately 0.28 for crystal B and G, respectively. In both crystal polymorphs of 2 and 3, crystals GB and G showed emission color changes by heating/melting/cooling cycles that were representative. By following the color changes in heating at the temperature below the melting point with X-ray diffraction measurements and X-ray crystallography, the single-crystal-to- single-crystal transformations from crystal GB to YG for 2 and from crystal B to G for 3 were revealed.",
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AB - 2,4-Trifluoromethylquinoline (TFMAQ) derivatives that have amine (1), methylamine (2), phenylamine (3), and dimethylamine (4) substituents at the 7-position of the quinoline ring were prepared and crystallized. Six crystals including the crystal polymorphs of 2 (crystal GB and YG) and 3 (crystal B and G) were obtained and characterized by X-ray crystallography. In solution, TFMAQ derivatives emitted relatively strong fluorescence (λf max=418-469 nm and φf(s)=0.23-0.60) depending on the solvent polarity. From Lippert-Mataga plots, δμ values in the range of 7.8-14 D were obtained. In the crystalline state, TFMAQ derivatives emitted at longer wavelengths (λfmax=464-530 nm) with lower intensity (φf(c)=0.01-0.28) than those in n-hexane solution. The polymorphous crystals of 2 and 3 emitted different colors: 2, λfmax=470 and 530 nm with φf(c)=0.04 and approximately 0.01 for crystal GB and YG, respectively; and 3, λ fmax=464 and 506 nm with φf(c)=0.28 and approximately 0.28 for crystal B and G, respectively. In both crystal polymorphs of 2 and 3, crystals GB and G showed emission color changes by heating/melting/cooling cycles that were representative. By following the color changes in heating at the temperature below the melting point with X-ray diffraction measurements and X-ray crystallography, the single-crystal-to- single-crystal transformations from crystal GB to YG for 2 and from crystal B to G for 3 were revealed.

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