Quantum chemical study of tautomeric equilibriums, intramolecular hydrogen bonds, and π-electron delocalization in the first singlet and triplet excited states of 2-selenoformyl-3-thioxo-propionaldehyde

IF 2.1 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Journal of Sulfur Chemistry Pub Date : 2023-03-01 DOI:10.1080/17415993.2023.2171292
Ramin Rafat , Ebrahim Nakhaei , Farshid Zargari , Faezeh Gorgichi , Alireza Nowroozi
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Abstract

In the present study, the tautomeric process, intramolecular hydrogen bonding (IMHB), and π-electron delocalization (π-ED) of 2-selenoformyl-3-thioxo-propionaldehyde (STP) in the first singlet and triplet excited states were investigated by CIS and TD-DFT methods. The relative energies of hydrogen-bonded tautomers in both excited states indicate that the thiol/enol conformers are the most/least stable forms. In this regard, a detailed analysis of various tautomeric equilibriums, different types of hydrogen bonds, and π-electron delocalization was performed. The electronic energies of different tautomers indicate the thermodynamic preference of thiol with respect to the other forms. Furthermore, the low activation energy barriers of thione⇄thiol equilibrium also show the kinetic preference of thiol. On the other hand, the estimation of different hydrogen bond energies emphasizes the stronger IMHB of enol. Moreover, the evaluation of π-ED by the structural parameter of Gilli (λ) represents the significance of electron mobility in the enol conformers. Consequently, the duality between the IMHB and π-ED with the thermodynamic stability order of tautomers indicates that the tautomeric phenomenons play a dominant role in determining the stability of the benchmark structures in both singlet and triplet excited states.

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2-硒代甲酰基-3-硫代丙醛第一单重态和三重态激发态的互变异构平衡、分子内氢键和π电子离域的量子化学研究
本研究采用CIS和TD-DFT方法研究了2-硒甲酰基-3-硫氧基丙醛(STP)在第一单线态和三线态激发态的互变异构过程、分子内氢键(IMHB)和π-电子离域(π-ED)。氢键互变异构体在两种激发态下的相对能量表明硫醇/烯醇构象异构体是最稳定/最不稳定的形式。在这方面,对各种互变异构平衡、不同类型的氢键和π-电子离域进行了详细分析。不同互变异构体的电子能表明硫醇相对于其他形式的热力学偏好。此外,硫酮的低活化能垒⇄硫醇平衡也显示出硫醇的动力学偏好。另一方面,对不同氢键能的估计强调了烯醇更强的IMHB。此外,通过Gilli(λ)的结构参数对π-ED的评价代表了烯醇构象中电子迁移率的重要性。因此,IMHB和π-ED之间的对偶性以及互变异构体的热力学稳定性顺序表明,互变异构现象在决定单重态和三重态激发态下基准结构的稳定性方面起着主导作用。图形摘要
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来源期刊
Journal of Sulfur Chemistry
Journal of Sulfur Chemistry CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
4.10
自引率
9.10%
发文量
38
审稿时长
6-12 weeks
期刊介绍: The Journal of Sulfur Chemistry is an international journal for the dissemination of scientific results in the rapidly expanding realm of sulfur chemistry. The journal publishes high quality reviews, full papers and communications in the following areas: organic and inorganic chemistry, industrial chemistry, materials and polymer chemistry, biological chemistry and interdisciplinary studies directly related to sulfur science. Papers outlining theoretical, physical, mechanistic or synthetic studies pertaining to sulfur chemistry are welcome. Hence the target audience is made up of academic and industrial chemists with peripheral or focused interests in sulfur chemistry. Manuscripts that truly define the aims of the journal include, but are not limited to, those that offer: a) innovative use of sulfur reagents; b) new synthetic approaches to sulfur-containing biomolecules, materials or organic and organometallic compounds; c) theoretical and physical studies that facilitate the understanding of sulfur structure, bonding or reactivity; d) catalytic, selective, synthetically useful or noteworthy transformations of sulfur containing molecules; e) industrial applications of sulfur chemistry; f) unique sulfur atom or molecule involvement in interfacial phenomena; g) descriptions of solid phase or combinatorial methods involving sulfur containing substrates. Submissions pertaining to related atoms such as selenium and tellurium are also welcome. Articles offering routine heterocycle formation through established reactions of sulfur containing substrates are outside the scope of the journal.
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