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Title: Computational study on the removal of photolabile protecting groups by photochemical reactions

Abstract

The application and versatility of photolabile protecting groups (PPGs) have continued to expand since their inception almost 50 years ago. In the present work we employ density functional theory (DFT) to characterize ground and excited state properties of several compounds with PPGs and to explore possible, controllable photodissociation reactions that remove these PPGs. The reaction mechanism is examined by analyzing the DFT results as well as dynamical simulations of nonadiabatic electron transfer reactions using multilayer multiconfiguration time-dependent Hartree theory. The photoexcited compounds appear to undergo ultrafast back electron transfer to the ground electronic state via internal conversion. For some compounds, the electronic-nuclear couplings facilitate sufficient photo energy transfer to the nuclear degrees of freedom that dominate the reaction coordinate, leading to the dissociation reaction that removes the PPGs.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]
  1. Univ. of Colorado, Denver, CO (United States). Dept. of Chemistry
  2. Univ. of Colorado, Denver, CO (United States). Dept. of Chemistry; Beijing Computational Science Research Center, Beijing (China)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1530606
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Computational and Theoretical Chemistry
Additional Journal Information:
Journal Volume: 1151; Journal Issue: C; Journal ID: ISSN 2210-271X
Publisher:
Elsevier
Country of Publication:
United States
Language:
English

Citation Formats

Yang, Chou-Hsun, Denne, Johanna, Reed, Scott, and Wang, Haobin. Computational study on the removal of photolabile protecting groups by photochemical reactions. United States: N. p., 2019. Web. doi:10.1016/j.comptc.2019.01.016.
Yang, Chou-Hsun, Denne, Johanna, Reed, Scott, & Wang, Haobin. Computational study on the removal of photolabile protecting groups by photochemical reactions. United States. doi:10.1016/j.comptc.2019.01.016.
Yang, Chou-Hsun, Denne, Johanna, Reed, Scott, and Wang, Haobin. Fri . "Computational study on the removal of photolabile protecting groups by photochemical reactions". United States. doi:10.1016/j.comptc.2019.01.016.
@article{osti_1530606,
title = {Computational study on the removal of photolabile protecting groups by photochemical reactions},
author = {Yang, Chou-Hsun and Denne, Johanna and Reed, Scott and Wang, Haobin},
abstractNote = {The application and versatility of photolabile protecting groups (PPGs) have continued to expand since their inception almost 50 years ago. In the present work we employ density functional theory (DFT) to characterize ground and excited state properties of several compounds with PPGs and to explore possible, controllable photodissociation reactions that remove these PPGs. The reaction mechanism is examined by analyzing the DFT results as well as dynamical simulations of nonadiabatic electron transfer reactions using multilayer multiconfiguration time-dependent Hartree theory. The photoexcited compounds appear to undergo ultrafast back electron transfer to the ground electronic state via internal conversion. For some compounds, the electronic-nuclear couplings facilitate sufficient photo energy transfer to the nuclear degrees of freedom that dominate the reaction coordinate, leading to the dissociation reaction that removes the PPGs.},
doi = {10.1016/j.comptc.2019.01.016},
journal = {Computational and Theoretical Chemistry},
issn = {2210-271X},
number = C,
volume = 1151,
place = {United States},
year = {2019},
month = {3}
}