Crystalline transformations of dinaphthyridinylamine derivatives with alteration of solid-state emission in response to external stimuli

Ryusuke Hagihara, Naomi Harada, Satoru Karasawa, Noboru Koga

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Dinaphthyridinylamine derivatives, (1,8Nap)2NR (R = H (1), Me (2) and Ph (3)), were prepared as fluorophores in response to external stimuli. From crystallization, single crystals (1) containing water molecules as crystal solvents and crystal polymorphs (3-α and 3-β) containing MeOH molecules were obtained. In the crystal packing of 1, a γ-herringbone (γ-HB) fashion with π-π interaction was observed. In contrast, the packing of 3-α was in a HB fashion with intermolecular CH-N interaction, while the packing of 3-β was in a slipped columnar fashion with π-π interaction between the naphthyridine planes. The observed difference of crystal packings influenced the solid-state emission spectra. Crystals 1, 2 and 3 showed piezochromic behaviors, in which by thoroughly grinding the crystals, the solid-state emission blue color (λfmax = ca. 450 nm) turned into yellowish green (λfmax = ca. 510 nm) for the amorphous solid. In addition, crystals 3-α and 3-β showed various phase transitions including single-crystal-to-single-crystal (SC-to-SC) transformation in response to external stimuli. Crystal 3-β desorbed the MeOH molecules under ambient atmosphere to provide crystal 3-β′ (λfmax = 449 nm), while the resulting crystal 3-β′ returned to crystal 3-β upon exposure to MeOH vapor, indicating vapochromic behavior. Furthermore, crystal 3-β′ was heated at ca. 160 °C to afford crystal 3-α (SC-to-SC transformation). The gummy oil in the resulting supercooled liquid (SCL) state after melting the crystals was scratched by using a fine wire at and above 80 °C (>Tg, glass temperature) to form crystal 3-α with blue emission (SCL-to-SC transformation).

Original languageEnglish
Pages (from-to)8825-8834
Number of pages10
JournalCrystEngComm
Volume17
Issue number46
DOIs
Publication statusPublished - 2015

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stimuli
Crystalline materials
Derivatives
solid state
Crystals
crystals
Single crystals
single crystals
Molecules
Naphthyridines
molecules
Fluorophores
Liquids
interactions
grinding
liquids
Crystallization
Polymorphism
Oils
Melting

All Science Journal Classification (ASJC) codes

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

Cite this

Crystalline transformations of dinaphthyridinylamine derivatives with alteration of solid-state emission in response to external stimuli. / Hagihara, Ryusuke; Harada, Naomi; Karasawa, Satoru; Koga, Noboru.

In: CrystEngComm, Vol. 17, No. 46, 2015, p. 8825-8834.

Research output: Contribution to journalArticle

Hagihara, Ryusuke ; Harada, Naomi ; Karasawa, Satoru ; Koga, Noboru. / Crystalline transformations of dinaphthyridinylamine derivatives with alteration of solid-state emission in response to external stimuli. In: CrystEngComm. 2015 ; Vol. 17, No. 46. pp. 8825-8834.
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abstract = "Dinaphthyridinylamine derivatives, (1,8Nap)2NR (R = H (1), Me (2) and Ph (3)), were prepared as fluorophores in response to external stimuli. From crystallization, single crystals (1) containing water molecules as crystal solvents and crystal polymorphs (3-α and 3-β) containing MeOH molecules were obtained. In the crystal packing of 1, a γ-herringbone (γ-HB) fashion with π-π interaction was observed. In contrast, the packing of 3-α was in a HB fashion with intermolecular CH-N interaction, while the packing of 3-β was in a slipped columnar fashion with π-π interaction between the naphthyridine planes. The observed difference of crystal packings influenced the solid-state emission spectra. Crystals 1, 2 and 3 showed piezochromic behaviors, in which by thoroughly grinding the crystals, the solid-state emission blue color (λfmax = ca. 450 nm) turned into yellowish green (λfmax = ca. 510 nm) for the amorphous solid. In addition, crystals 3-α and 3-β showed various phase transitions including single-crystal-to-single-crystal (SC-to-SC) transformation in response to external stimuli. Crystal 3-β desorbed the MeOH molecules under ambient atmosphere to provide crystal 3-β′ (λfmax = 449 nm), while the resulting crystal 3-β′ returned to crystal 3-β upon exposure to MeOH vapor, indicating vapochromic behavior. Furthermore, crystal 3-β′ was heated at ca. 160 °C to afford crystal 3-α (SC-to-SC transformation). The gummy oil in the resulting supercooled liquid (SCL) state after melting the crystals was scratched by using a fine wire at and above 80 °C (>Tg, glass temperature) to form crystal 3-α with blue emission (SCL-to-SC transformation).",
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AB - Dinaphthyridinylamine derivatives, (1,8Nap)2NR (R = H (1), Me (2) and Ph (3)), were prepared as fluorophores in response to external stimuli. From crystallization, single crystals (1) containing water molecules as crystal solvents and crystal polymorphs (3-α and 3-β) containing MeOH molecules were obtained. In the crystal packing of 1, a γ-herringbone (γ-HB) fashion with π-π interaction was observed. In contrast, the packing of 3-α was in a HB fashion with intermolecular CH-N interaction, while the packing of 3-β was in a slipped columnar fashion with π-π interaction between the naphthyridine planes. The observed difference of crystal packings influenced the solid-state emission spectra. Crystals 1, 2 and 3 showed piezochromic behaviors, in which by thoroughly grinding the crystals, the solid-state emission blue color (λfmax = ca. 450 nm) turned into yellowish green (λfmax = ca. 510 nm) for the amorphous solid. In addition, crystals 3-α and 3-β showed various phase transitions including single-crystal-to-single-crystal (SC-to-SC) transformation in response to external stimuli. Crystal 3-β desorbed the MeOH molecules under ambient atmosphere to provide crystal 3-β′ (λfmax = 449 nm), while the resulting crystal 3-β′ returned to crystal 3-β upon exposure to MeOH vapor, indicating vapochromic behavior. Furthermore, crystal 3-β′ was heated at ca. 160 °C to afford crystal 3-α (SC-to-SC transformation). The gummy oil in the resulting supercooled liquid (SCL) state after melting the crystals was scratched by using a fine wire at and above 80 °C (>Tg, glass temperature) to form crystal 3-α with blue emission (SCL-to-SC transformation).

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