Computational detangling chalcogen elements substitutions associated ESDPT mechanism for oxazolinyl-substituted hydroxyfluorene derivatives

Jiahe Chen; Jinfeng Zhao

doi:10.1016/j.saa.2024.125493

Computational detangling chalcogen elements substitutions associated ESDPT mechanism for oxazolinyl-substituted hydroxyfluorene derivatives

Spectrochim Acta A Mol Biomol Spectrosc. 2024 Nov 26:328:125493. doi: 10.1016/j.saa.2024.125493. Online ahead of print.

Authors

Jiahe Chen¹, Jinfeng Zhao²

Affiliations

¹ College of Physical Science and Technology, Shenyang Normal University, Shenyang 110034, China; School of Physics, Liaoning University, Shenyang 110034, China.
² College of Physical Science and Technology, Shenyang Normal University, Shenyang 110034, China; International Cooperative Joint Laboratory of Condensed Matter Physics, Shenyang Normal University, Shenyang, 110034, China; School of Physics, Liaoning University, Shenyang 110034, China. Electronic address: jfzhao1990112@163.com.

PMID: 39603084
DOI: 10.1016/j.saa.2024.125493

Abstract

In view of the distinguished photochemical and photobiological characteristics of oxazolinyl-substituted hydroxyfluorene and its derivatives, herein, we mainly focus on probing into excited state behaviors of the novel 9,9-dimethyl-3,6-dihydroxy-2,7-bis(4,5-dihydro-4,4-dimethyl-2-oxazolyl) fluorene (Oxa-OH) derivatives. In light of the significant effects resulting from substituting oxygen elements, three Oxa-OH derivatives (i.e., Oxa-OO, Oxa-SS and Oxa-SeSe fluorophores) are considered in this work. For these three different fluorophores, we detangle the effects of atomic electronegativity and charge recombination related to oxygen elements in excited state double proton transfer (ESDPT) processes. Because of the low potential energy barriers, we confirm the ESDPT happens by the sequential type. Based on heterosubstituted Oxa-OS and Oxa-OSe compounds, we further verify the chalcogen atomic-electronegativity-regulated stepwise ESDPT mechanism. We sincerely wish our work could provide a theoretical reference for proving this novel mechanism of ESDPT experimentally.

Keywords: Chalcogen atomic electronegativity; Charge redistribution; Excited state double proton transfer; Hydrogen bonding interaction; Potential energy surface.