Excited-state intramolecular double proton transfer mechanism associated with solvent polarity for 9,9-dimethyl-3,6-dihydroxy-2,7-bis(4,5-dihydro-4,4-dimethyl-2-oxazolyl)fluorene compound

Abstract

Excited-state intramolecular proton transfer (ESIPT) has been well investigated in recent years, whereas we investigated the system containing double hydrogen bonds. We explore the influence of solvent polarity on the proton transfer mechanism for 9,9-dimethyl-3,6-dihydroxy-2,7-bis(4,5-dihydro-4,4-dimethyl-2-oxazolyl)fluorene compound ((Oxa-OH)₂). We consider three solvents with different polarities: cyclohexane, chloroform and acetonitrile. Various analytical methods indicate that hydrogen bonding is enhanced in the first excited state, which facilitates the proton transfer within the excited-state molecule. The frontier molecular orbital theory is employed to demonstrate that the system is subjected to photoexcitation to generate charge density redistribution. Three-dimensional potential energy surfaces are also constructed along the direction of hydrogen bond elongated, and their corresponding projection in the X-axis and Y-axis planes are plotted. The comparison of the potential barriers and the transition state structures of each proton transfer path reveals the excited-state intramolecular single proton transfer mechanism of the system. By comparing the potential barriers in different solvents, we also propose a mechanism that can modulate the excited-state proton transfer by changing the solvent polarity.

GRAPHICAL ABSTRACT

KEYWORDS:

• Excited-state proton transfer
• intramolecular hydrogen bond
• potential energy surfaces
• solvent polarity

Acknowledgements

We are grateful to the China Postdoctoral Science Foundation (Grant No: 2020M682154), the National Natural Science Foundation of China (Grant No: 21873114), the LiaoNing Revitalization Talents Program (grant number XLYC1807162), and the Shenyang High-level Innovative Talents Program (RC200565).

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

We are grateful to the China Postdoctoral Science Foundation [grant number 2020M682154]; the National Natural Science Foundation of China [grant number 21873114]; the LiaoNing Revitalization Talents Program [grant number XLYC1807162]; the Shenyang High-level Innovative Talents Program [grant number RC200565].