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 Y. Li; Pi Tai Chou

doi:10.1021/jacs.9b02765

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 Y. Li, Pi Tai Chou

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

79 Citations (Scopus)

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 language	English
Pages (from-to)	9885-9894
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	141
Issue number	25
DOIs	https://doi.org/10.1021/jacs.9b02765
Publication status	Published - 2019 Jun 26

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.9b02765

Cite this

@article{38635491bd564642bafc8ab092825a76,

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

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.",

author = "Liu, {Zong Ying} and Hu, {Jiun Wei} and Huang, {Chun Hao} and Huang, {Teng Hsing} and Chen, {Deng Gao} and Ho, {Ssu Yu} and Chen, {Kew Yu} and Li, {Elise Y.} and Chou, {Pi Tai}",

note = "Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = jun,

day = "26",

doi = "10.1021/jacs.9b02765",

language = "English",

volume = "141",

pages = "9885--9894",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "25",

}

TY - JOUR

T1 - Sulfur-Based Intramolecular Hydrogen-Bond

T2 - Excited-State Hydrogen-Bond On/Off Switch with Dual Room-Temperature Phosphorescence

AU - Liu, Zong Ying

AU - Hu, Jiun Wei

AU - Huang, Chun Hao

AU - Huang, Teng Hsing

AU - Chen, Deng Gao

AU - Ho, Ssu Yu

AU - Chen, Kew Yu

AU - Li, Elise Y.

AU - Chou, Pi Tai

PY - 2019/6/26

Y1 - 2019/6/26

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85068195502&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85068195502&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b02765

DO - 10.1021/jacs.9b02765

M3 - Article

C2 - 31244136

AN - SCOPUS:85068195502

SN - 0002-7863

VL - 141

SP - 9885

EP - 9894

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 25

ER -

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

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 1935633: Experimental Crystal Structure Determination

CCDC 1935634: Experimental Crystal Structure Determination

CCDC 1935632: Experimental Crystal Structure Determination

Cite this

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

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1935633: Experimental Crystal Structure Determination

CCDC 1935634: Experimental Crystal Structure Determination

CCDC 1935632: Experimental Crystal Structure Determination

Cite this