Highly Selective Aluminum(III) Ion Sensing with Luminescent Iridium(III) Complexes Bearing a Distorted 2,2′-Bipyridine-3,3′-diol Moiety Utilizing a Rigidified Seven-Membered Chelate Ring

Yota Suzuki, Ibuki Mizuno, Yui Tabei, Yuri Fujioka, Kazuteru Shinozaki, Tomoaki Sugaya, Koji Ishihara

Research output: Contribution to journalArticle

Abstract

To create an ion sensor utilizing a rigidified seven-membered chelate ring, we developed two Ir(III) complexes with 2,2′-bipyridine-3,3′-diol (bpy(OH)2, bpydL) ligands as reaction centers, namely Ir1 ([Ir(ppy)2{bpy(O-)(OH)}], ppy = 2-phenylpyridine) and Ir2 ([Ir(bzq)2{bpy(O-)(OH)}], bzq = benzo[h]quinoline), and evaluated their reactivities toward metal ions by spectrophotometry. When they are reacted with Al3+, these complexes exhibit dramatic enhancements in emission intensity (775-fold for Ir1 and 51.0-fold for Ir2) and distinct orange to green changes in emission color. The reactions of Ir1 and Ir2 with Al3+ were found to barely be affected by nearly all common metal ions. We conclude that these high selectivities arise from the high affinities of the (O,O) atoms in bpydL for hard metal ions and the increased strain of the seven-membered chelate ring due to the coordination of bpydL to the Ir(III) center in each complex, which excludes large metal ions out of the chelate ring.

Original languageEnglish
Pages (from-to)9663-9671
Number of pages9
JournalInorganic Chemistry
Volume58
Issue number15
DOIs
Publication statusPublished - 2019 Aug 5

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Bearings (structural)
Iridium
iridium
Aluminum
chelates
Metal ions
metal ions
Ions
aluminum
rings
ions
quinoline
Spectrophotometry
spectrophotometry
Heavy ions
affinity
reactivity
selectivity
Ligands
Color

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Highly Selective Aluminum(III) Ion Sensing with Luminescent Iridium(III) Complexes Bearing a Distorted 2,2′-Bipyridine-3,3′-diol Moiety Utilizing a Rigidified Seven-Membered Chelate Ring. / Suzuki, Yota; Mizuno, Ibuki; Tabei, Yui; Fujioka, Yuri; Shinozaki, Kazuteru; Sugaya, Tomoaki; Ishihara, Koji.

In: Inorganic Chemistry, Vol. 58, No. 15, 05.08.2019, p. 9663-9671.

Research output: Contribution to journalArticle

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T1 - Highly Selective Aluminum(III) Ion Sensing with Luminescent Iridium(III) Complexes Bearing a Distorted 2,2′-Bipyridine-3,3′-diol Moiety Utilizing a Rigidified Seven-Membered Chelate Ring

AU - Suzuki, Yota

AU - Mizuno, Ibuki

AU - Tabei, Yui

AU - Fujioka, Yuri

AU - Shinozaki, Kazuteru

AU - Sugaya, Tomoaki

AU - Ishihara, Koji

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N2 - To create an ion sensor utilizing a rigidified seven-membered chelate ring, we developed two Ir(III) complexes with 2,2′-bipyridine-3,3′-diol (bpy(OH)2, bpydL) ligands as reaction centers, namely Ir1 ([Ir(ppy)2{bpy(O-)(OH)}], ppy = 2-phenylpyridine) and Ir2 ([Ir(bzq)2{bpy(O-)(OH)}], bzq = benzo[h]quinoline), and evaluated their reactivities toward metal ions by spectrophotometry. When they are reacted with Al3+, these complexes exhibit dramatic enhancements in emission intensity (775-fold for Ir1 and 51.0-fold for Ir2) and distinct orange to green changes in emission color. The reactions of Ir1 and Ir2 with Al3+ were found to barely be affected by nearly all common metal ions. We conclude that these high selectivities arise from the high affinities of the (O,O) atoms in bpydL for hard metal ions and the increased strain of the seven-membered chelate ring due to the coordination of bpydL to the Ir(III) center in each complex, which excludes large metal ions out of the chelate ring.

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