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
N1 - Funding Information:
We appreciate the Ministry of Science and Technology (MOST 107-2628-M-002-017, MOST 107-2113-M-035-003, and MOST 106-2113-M-003-010-MY3), Taiwan, for their generous support. We thank National Center for High-performance Computing (NCHC) of Taiwan for the help on computational resources.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
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.
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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 -