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 | |
| Publication status | Published - 2019 Jun 26 |
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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 journal › Article
}
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 Yu-Tzu
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
VL - 141
SP - 9885
EP - 9894
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 25
ER -