A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation

Liu, Fengyi; Liu, Yajun; Vico, Luca De; Lindh, Roland

doi:10.1016/j.cplett.2009.11.009

Cited by 50 publications

(65 citation statements)

References 28 publications

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“…The mechanism which is non-CT stepwise for the neutral species is for O À -TDO a CT mechanism (either CIEEL or CTIL), where an electron is transferred from the electron-donating fragment, formed by a charged hetero-atom and an electron reservoir p aromatic system, to the dioxetanone moiety ( Figure 7). [18] While the reaction for the H-TDO and HO-TDO species can strictly be associated with the www.chemphyschem.org a configuration in which the s and s* orbitals are occupied by three electrons, thus destabilizing the bond and lowering the activation barrier for the fragmentation process. This is an important mechanism in making the reaction energetically feasible in a living species.…”

Section: The Electron-donating Fragmentmentioning

confidence: 99%

“…According to Greenman, rather large active spaces, beyond the capacity of standard methods, have to be employed to safeguard quantitative accuracy. However, the calculated results presented on 1,2-dioxetane, [16] dioxetanone [17] and thiazol-substituted dioxetanone [18] were done at the MS-CASPT2/SA-CASSCF level of theory in association with appropriately selected active spaces. For the theoretical study of the luciferin-luciferase system further considerations and assumptions are required.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The decomposition mechanism of the dioxetanone compounds is the key point to understand how the ground-state reactant leads to the excited-state product. Therefore we have studied the mechanism starting from the small model compounds, 1,2-dioxetane, [16] dioxetanone, [17] and thiazol-substituted dioxetanone [18] (Figure 3). In this series of theoretical studies we hoped to rationalize the importance of each individual part of the firefly dioxetanone system.…”

Section: Chemiluminescence By Chemical Functionalitiesmentioning

confidence: 99%

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The Chemistry of Bioluminescence: An Analysis of Chemical Functionalities

Navizet¹,

Liu²,

Ferré³

et al. 2011

ChemPhysChem

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115

175

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Firefly luciferase is one of the most studied bioluminescent systems, both theoretically and experimentally. Herein we review the current understanding of the bioluminescent process from a chemical functionality perspective based on those investigations. Three key components are emphasized: the chemiluminophore, the electron-donating fragment, and how these are affected by the substrate-enzyme interaction. The understanding is based on details of how the peroxide -O-O- bond supports the production of electronically excited products and how the charge-transfer (CT) mechanism, with the aid of an electron-donating group, lowers the activation barrier to support a reaction occurs in living organisms. For the substrate-enzyme complex it is demonstrated that the enzyme can affect the hydrogen-bonding around the CT-controlling group, resulting in a mechanism for color modulation. Finally, we analyse other luciferin-luciferase systems and compare them to the key chemical functionalities of the fragments of the luciferin-luciferase complex with respect to similarities and differences.

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Section: The Electron-donating Fragmentmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Chemiluminescence By Chemical Functionalitiesmentioning

confidence: 99%

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The Chemistry of Bioluminescence: An Analysis of Chemical Functionalities

Navizet¹,

Liu²,

Ferré³

et al. 2011

ChemPhysChem

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115

175

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“…In this process two points have been less fully examined. One is the formation and decomposition mechanisms of the actual firefly DO, although the analogous small molecules dioxetane and dioxetanone have been studied extensively [9][10][11][12][13][14]. A second is the ultimate conclusion about the relationship between the wide range of bioluminescent colors and the structure of the light emitter.…”

Section: Introductionmentioning

confidence: 99%

The formation and decomposition of firefly dioxetanone

Min

Ren

et al. 2011

Chemical Physics Letters

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“…Recently, the mechanism of 1,2-dioxetane has been established by these means to be of biradical type. 21 Moreover, accurate theoretical approaches have been employed successfully to determine the chemiluminescence mechanism of dioxetanone, [22][23][24] small models of the Firefly luciferin and coelenterazine, 25,26 and the Firefly luciferin 27,28 and coelenterazine 29,30 systems themselves. Quantum chemistry may, therefore, be applied to study how photochemical processes can be induced chemically "in the dark".…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of the dark photochemistry of 1,3-butadiene via the chemiexcitation of Dewar dioxetane

Farahani

Lundberg

Lindh

et al. 2015

Phys. Chem. Chem. Phys.

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Excited-state chemistry is usually ascribed to photo-induced processes, such as fluorescence, phosphorescence, and photochemistry, or to bio-and chemiluminescence, in which light emission is originated by a chemical reaction. A third class of excited-state chemistry, however, is possible that promotes photochemical phenomena by chemienergizing certain chemical groups without light -chemiexcitation. By studying Dewar dioxetane, which can be viewed as the combination of 1,2-dioxetane and 1,3-butadiene, we show here how the isomerization * To whom correspondence should be addressed † Uppsala ‡ València ¶ UC 3 1 channel that characterizes the photo-induced chemistry of 1,3-butadiene can be reached at a later stage after the thermal decomposition of the dioxetane moiety. Multi-reference multiconfigurational quantum chemistry methods and accurate reaction-path computational strategies were used to determine the reaction coordinate that first decomposes the dioxetane, next transfers non-adiabatically the state from the ground to the excited state, and finally brings the system into the photochemical channel of the 1,3-butadiene group. With the present study, we open a new area of research within computational photochemistry to study chemically-induced excited-state chemistry that is difficult to tackle experimentally due to the short-lived character of the species involved in the process. The findings shall be of relevance to unveil "dark" photochemistry mechanisms which might operate in biological systems in conditions of lack of light to allow reactions that are typical of photo-induced phenomena.

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A CASSCF/CASPT2 approach to the decomposition of thiazole-substituted dioxetanone: Substitution effects and charge-transfer induced electron excitation

Cited by 50 publications

References 28 publications

The Chemistry of Bioluminescence: An Analysis of Chemical Functionalities

The Chemistry of Bioluminescence: An Analysis of Chemical Functionalities

The formation and decomposition of firefly dioxetanone

Theoretical study of the dark photochemistry of 1,3-butadiene via the chemiexcitation of Dewar dioxetane

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