Crystal structures, thermal properties, and emission behaviors of N, N -R-phenyl-7-amino-2,4-trifluoromethylquinoline derivatives: Supercooled liquid-to-crystal transformation induced by mechanical stimuli

Satoru Karasawa, Ryusuke Hagihara, Yuichiro Abe, Naomi Harada, Jun Ichi Todo, Noboru Koga

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

N,N-R-Phenyl-7-amino-2,4-trifluoromethylquinoline derivatives (R = Me (1), Et (2), isopropyl (3), and Ph (4)) were prepared as a new type of fluorophore responsive to external stimuli. 1, 2, 3, and 4 were obtained as single crystals including three crystal polymorphs (1, 1β, and 1γ) of 1 and two (2 and 2β) of 2. In 4, a phase transition from 4173 and 4 90 between 173 and 90 K was observed. The solid-state emission showed a red shift by 30-58 nm compared with the emission in n-hexane, and their emission properties depended on the molecular arrangements. The modes of molecular arrangements for 1, 1β, and 1γ were a slipped parallel (SP), head-to-tail γ-type herringbone (HT-γ-HB), and head-to-head γ-type herringbone (HH-γ-HB); those for 2 and 2β were HT-γ-HB and head-to-tail dimer (HT-dimer), and that for 3 was head-to-tail columnar (HTC). 4173 and 490 were similar HT-γ-HB. The crystal-to-crystal transformations from 1γ to 1β and from 2β to 2 were observed by heating and grinding the crystal, respectively, with emittance changes. After melting, on cooling, all crystals formed supercooled liquid (SCL) and then glass states. In the SCL state, molecules were amorphous and were quickly crystallized by a mechanical stimulus such as scratching. By taking advantage of the difference of emitting intensity between the SCL and the crystal states for 1, "writing" and "erasing" of a letter with scratching and heating, respectively, were demonstrated.

Original languageEnglish
Pages (from-to)2468-2478
Number of pages11
JournalCrystal Growth and Design
Volume14
Issue number5
DOIs
Publication statusPublished - May 7 2014

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thermal emission
stimuli
Thermodynamic properties
thermodynamic properties
Crystal structure
Derivatives
Crystals
crystal structure
Liquids
liquids
crystals
Heating
Liquid Crystals
Fluorophores
Polymorphism
heating
Dimers
grinding
emittance
Hexane

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Crystal structures, thermal properties, and emission behaviors of N, N -R-phenyl-7-amino-2,4-trifluoromethylquinoline derivatives : Supercooled liquid-to-crystal transformation induced by mechanical stimuli. / Karasawa, Satoru; Hagihara, Ryusuke; Abe, Yuichiro; Harada, Naomi; Todo, Jun Ichi; Koga, Noboru.

In: Crystal Growth and Design, Vol. 14, No. 5, 07.05.2014, p. 2468-2478.

Research output: Contribution to journalArticle

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abstract = "N,N-R-Phenyl-7-amino-2,4-trifluoromethylquinoline derivatives (R = Me (1), Et (2), isopropyl (3), and Ph (4)) were prepared as a new type of fluorophore responsive to external stimuli. 1, 2, 3, and 4 were obtained as single crystals including three crystal polymorphs (1, 1β, and 1γ) of 1 and two (2 and 2β) of 2. In 4, a phase transition from 4173 and 4 90 between 173 and 90 K was observed. The solid-state emission showed a red shift by 30-58 nm compared with the emission in n-hexane, and their emission properties depended on the molecular arrangements. The modes of molecular arrangements for 1, 1β, and 1γ were a slipped parallel (SP), head-to-tail γ-type herringbone (HT-γ-HB), and head-to-head γ-type herringbone (HH-γ-HB); those for 2 and 2β were HT-γ-HB and head-to-tail dimer (HT-dimer), and that for 3 was head-to-tail columnar (HTC). 4173 and 490 were similar HT-γ-HB. The crystal-to-crystal transformations from 1γ to 1β and from 2β to 2 were observed by heating and grinding the crystal, respectively, with emittance changes. After melting, on cooling, all crystals formed supercooled liquid (SCL) and then glass states. In the SCL state, molecules were amorphous and were quickly crystallized by a mechanical stimulus such as scratching. By taking advantage of the difference of emitting intensity between the SCL and the crystal states for 1, {"}writing{"} and {"}erasing{"} of a letter with scratching and heating, respectively, were demonstrated.",
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T1 - Crystal structures, thermal properties, and emission behaviors of N, N -R-phenyl-7-amino-2,4-trifluoromethylquinoline derivatives

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AU - Karasawa, Satoru

AU - Hagihara, Ryusuke

AU - Abe, Yuichiro

AU - Harada, Naomi

AU - Todo, Jun Ichi

AU - Koga, Noboru

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N2 - N,N-R-Phenyl-7-amino-2,4-trifluoromethylquinoline derivatives (R = Me (1), Et (2), isopropyl (3), and Ph (4)) were prepared as a new type of fluorophore responsive to external stimuli. 1, 2, 3, and 4 were obtained as single crystals including three crystal polymorphs (1, 1β, and 1γ) of 1 and two (2 and 2β) of 2. In 4, a phase transition from 4173 and 4 90 between 173 and 90 K was observed. The solid-state emission showed a red shift by 30-58 nm compared with the emission in n-hexane, and their emission properties depended on the molecular arrangements. The modes of molecular arrangements for 1, 1β, and 1γ were a slipped parallel (SP), head-to-tail γ-type herringbone (HT-γ-HB), and head-to-head γ-type herringbone (HH-γ-HB); those for 2 and 2β were HT-γ-HB and head-to-tail dimer (HT-dimer), and that for 3 was head-to-tail columnar (HTC). 4173 and 490 were similar HT-γ-HB. The crystal-to-crystal transformations from 1γ to 1β and from 2β to 2 were observed by heating and grinding the crystal, respectively, with emittance changes. After melting, on cooling, all crystals formed supercooled liquid (SCL) and then glass states. In the SCL state, molecules were amorphous and were quickly crystallized by a mechanical stimulus such as scratching. By taking advantage of the difference of emitting intensity between the SCL and the crystal states for 1, "writing" and "erasing" of a letter with scratching and heating, respectively, were demonstrated.

AB - N,N-R-Phenyl-7-amino-2,4-trifluoromethylquinoline derivatives (R = Me (1), Et (2), isopropyl (3), and Ph (4)) were prepared as a new type of fluorophore responsive to external stimuli. 1, 2, 3, and 4 were obtained as single crystals including three crystal polymorphs (1, 1β, and 1γ) of 1 and two (2 and 2β) of 2. In 4, a phase transition from 4173 and 4 90 between 173 and 90 K was observed. The solid-state emission showed a red shift by 30-58 nm compared with the emission in n-hexane, and their emission properties depended on the molecular arrangements. The modes of molecular arrangements for 1, 1β, and 1γ were a slipped parallel (SP), head-to-tail γ-type herringbone (HT-γ-HB), and head-to-head γ-type herringbone (HH-γ-HB); those for 2 and 2β were HT-γ-HB and head-to-tail dimer (HT-dimer), and that for 3 was head-to-tail columnar (HTC). 4173 and 490 were similar HT-γ-HB. The crystal-to-crystal transformations from 1γ to 1β and from 2β to 2 were observed by heating and grinding the crystal, respectively, with emittance changes. After melting, on cooling, all crystals formed supercooled liquid (SCL) and then glass states. In the SCL state, molecules were amorphous and were quickly crystallized by a mechanical stimulus such as scratching. By taking advantage of the difference of emitting intensity between the SCL and the crystal states for 1, "writing" and "erasing" of a letter with scratching and heating, respectively, were demonstrated.

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