The excited-state heterolysis of acridinol-based derivatives leads to the release of the OH- ion and the formation of the corresponding acridinium cations. To evaluate the parameters that control the reaction barriers, the kinetics of excited-state OH- release from a series of acridinol photobases were studied using transient absorption spectroscopy. The rate constants were obtained in three solvents (methanol, butanol, and isobutanol), and the data were modeled using Marcus theory. The intrinsic reorganization energies obtained from these fits were found to correlate well with the solvent reorganization energies calculated using dielectric continuum model, suggesting that the excited-state OH- release occurs along the solvent reaction coordinate. Furthermore, the ability of acridinol photobases to photoinitiate chemical reactions was demonstrated using the Michael reaction between dimethylmalonate and nitrostyrene.
Source:
Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 2017, 121, 2, 448-457
Publisher:
Amer Chemical Soc, Washington
Funding / projects:
Petroleum Research Fund [54436-ND4]
National Science Foundation [1055397]
Note:
This is the peer-reviewed version of the following article:Xie, Y.; Ilic, S.; Skaro, S.; Maslak, V.; Glusac, K. D. Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases. Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Th 2017, 121 (2), 448–457. https://doi.org/10.1021/acs.jpca.6b10980
TY - JOUR
AU - Xie, Yun
AU - Ilic, Stefan
AU - Škaro, Sanja
AU - Maslak, Veselin
AU - Glušač, Ksenija D.
PY - 2017
UR - https://cherry.chem.bg.ac.rs/handle/123456789/2977
AB - The excited-state heterolysis of acridinol-based derivatives leads to the release of the OH- ion and the formation of the corresponding acridinium cations. To evaluate the parameters that control the reaction barriers, the kinetics of excited-state OH- release from a series of acridinol photobases were studied using transient absorption spectroscopy. The rate constants were obtained in three solvents (methanol, butanol, and isobutanol), and the data were modeled using Marcus theory. The intrinsic reorganization energies obtained from these fits were found to correlate well with the solvent reorganization energies calculated using dielectric continuum model, suggesting that the excited-state OH- release occurs along the solvent reaction coordinate. Furthermore, the ability of acridinol photobases to photoinitiate chemical reactions was demonstrated using the Michael reaction between dimethylmalonate and nitrostyrene.
PB - Amer Chemical Soc, Washington
T2 - Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
T1 - Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases
VL - 121
IS - 2
SP - 448
EP - 457
DO - 10.1021/acs.jpca.6b10980
ER -
@article{
author = "Xie, Yun and Ilic, Stefan and Škaro, Sanja and Maslak, Veselin and Glušač, Ksenija D.",
year = "2017",
abstract = "The excited-state heterolysis of acridinol-based derivatives leads to the release of the OH- ion and the formation of the corresponding acridinium cations. To evaluate the parameters that control the reaction barriers, the kinetics of excited-state OH- release from a series of acridinol photobases were studied using transient absorption spectroscopy. The rate constants were obtained in three solvents (methanol, butanol, and isobutanol), and the data were modeled using Marcus theory. The intrinsic reorganization energies obtained from these fits were found to correlate well with the solvent reorganization energies calculated using dielectric continuum model, suggesting that the excited-state OH- release occurs along the solvent reaction coordinate. Furthermore, the ability of acridinol photobases to photoinitiate chemical reactions was demonstrated using the Michael reaction between dimethylmalonate and nitrostyrene.",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",
title = "Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases",
volume = "121",
number = "2",
pages = "448-457",
doi = "10.1021/acs.jpca.6b10980"
}
Xie, Y., Ilic, S., Škaro, S., Maslak, V.,& Glušač, K. D.. (2017). Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases. in Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Amer Chemical Soc, Washington., 121(2), 448-457.
https://doi.org/10.1021/acs.jpca.6b10980
Xie Y, Ilic S, Škaro S, Maslak V, Glušač KD. Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases. in Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2017;121(2):448-457.
doi:10.1021/acs.jpca.6b10980 .
Xie, Yun, Ilic, Stefan, Škaro, Sanja, Maslak, Veselin, Glušač, Ksenija D., "Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases" in Journal of Physical Chemistry. Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 121, no. 2 (2017):448-457,
https://doi.org/10.1021/acs.jpca.6b10980 . .
