Sulfur-Based Intramolecular Hydrogen-Bond: Excited-State Hydrogen-Bond On/Off Switch with Dual Room-Temperature Phosphorescence

Zong Ying Liu, Jiun Wei Hu, Chun Hao Huang, Teng Hsing Huang, Deng Gao Chen, Ssu Yu Ho, Kew Yu Chen, Elise Yu-Tzu Li, Pi Tai Chou

Research output: Contribution to journalArticle

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Abstract

We report O-H-S hydrogen-bond (H-bond) formation and its excited-state intramolecular H-bond on/off reaction unveiled by room-temperature phosphorescence (RTP). In this seminal work, this phenomenon is demonstrated with 7-hydroxy-2,2-dimethyl-2,3-dihydro-1H-indene-1-thione (DM-7HIT), which possesses a strong polar (hydroxy)-dispersive (thione) type H-bond. Upon excitation, DM-7HIT exhibits anomalous dual RTP with maxima at 550 and 685 nm. This study found that the lowest lying excited state (S1) of DM-7HIT is a sulfur nonbonding (n) to π∗ transition, which undergoes O-H bond flipping from S1(nπ*) to the non-H-bonded S′1(nπ*) state, followed by intersystem crossing and internal conversion to populate the T′1(nπ*) state. Fast H-bond on/off switching then takes place between T′1(nπ*) and T1(nπ*), forming a pre-equilibrium that affords both the T′1(nπ*, 685 nm) and T1(nπ*, 550 nm) RTP. The generality of the sulfur H-bond on/off switching mechanism, dubbed a molecule wiper, was rigorously evaluated with a variety of other H-bonded thiones, and these results open a new chapter in the chemistry of hydrogen bonds.

Original languageEnglish
Pages (from-to)9885-9894
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number25
DOIs
Publication statusPublished - 2019 Jun 26

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Phosphorescence
Sulfur
Excited states
Hydrogen
Hydrogen bonds
Switches
Thiones
Temperature
Molecules

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Sulfur-Based Intramolecular Hydrogen-Bond : Excited-State Hydrogen-Bond On/Off Switch with Dual Room-Temperature Phosphorescence. / Liu, Zong Ying; Hu, Jiun Wei; Huang, Chun Hao; Huang, Teng Hsing; Chen, Deng Gao; Ho, Ssu Yu; Chen, Kew Yu; Li, Elise Yu-Tzu; Chou, Pi Tai.

In: Journal of the American Chemical Society, Vol. 141, No. 25, 26.06.2019, p. 9885-9894.

Research output: Contribution to journalArticle

Liu, Zong Ying ; Hu, Jiun Wei ; Huang, Chun Hao ; Huang, Teng Hsing ; Chen, Deng Gao ; Ho, Ssu Yu ; Chen, Kew Yu ; Li, Elise Yu-Tzu ; Chou, Pi Tai. / Sulfur-Based Intramolecular Hydrogen-Bond : Excited-State Hydrogen-Bond On/Off Switch with Dual Room-Temperature Phosphorescence. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 25. pp. 9885-9894.
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