Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases
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.
Source:
Journal of Physical Chemistry A, 2017, 121, 2, 448-457Publisher:
- Amer Chemical Soc, Washington
Funding / projects:
- National Science Foundation [1055397]
- Petroleum Research Fund [54436-ND4]
DOI: 10.1021/acs.jpca.6b10980
ISSN: 1089-5639
PubMed: 27991787
WoS: 000392554400004
Scopus: 2-s2.0-85036641220
Collections
Institution/Community
Institut za molekularnu genetiku i genetičko inženjerstvoTY - JOUR AU - Xie, Yun AU - Ilić, Stefan AU - Škaro Bogojević, Sanja AU - Maslak, Veselin AU - Glusac, Ksenija D. PY - 2017 UR - https://imagine.imgge.bg.ac.rs/handle/123456789/998 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 A T1 - Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases EP - 457 IS - 2 SP - 448 VL - 121 DO - 10.1021/acs.jpca.6b10980 ER -
@article{ author = "Xie, Yun and Ilić, Stefan and Škaro Bogojević, Sanja and Maslak, Veselin and Glusac, 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 A", title = "Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases", pages = "457-448", number = "2", volume = "121", doi = "10.1021/acs.jpca.6b10980" }
Xie, Y., Ilić, S., Škaro Bogojević, S., Maslak, V.,& Glusac, K. D.. (2017). Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases. in Journal of Physical Chemistry A Amer Chemical Soc, Washington., 121(2), 448-457. https://doi.org/10.1021/acs.jpca.6b10980
Xie Y, Ilić S, Škaro Bogojević S, Maslak V, Glusac KD. Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases. in Journal of Physical Chemistry A. 2017;121(2):448-457. doi:10.1021/acs.jpca.6b10980 .
Xie, Yun, Ilić, Stefan, Škaro Bogojević, Sanja, Maslak, Veselin, Glusac, Ksenija D., "Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases" in Journal of Physical Chemistry A, 121, no. 2 (2017):448-457, https://doi.org/10.1021/acs.jpca.6b10980 . .