重新审视基质分离简单海因的结构、振动和光化学数据 - 共同特征和取代基效应

IF 0.6 4区 物理与天体物理 Q4 PHYSICS, APPLIED Low Temperature Physics Pub Date : 2024-09-04 DOI:10.1063/10.0028129
Rui Fausto, Gulce O. Ildiz, Bernardo A. Nogueira
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引用次数: 0

摘要

以我们之前报告的各个化合物的低温基质分离红外光谱和电子结构量子化学数据为基础,从比较全面的角度回顾了一系列简单海因(母海因、1-甲基海因、5-甲基海因和 5-乙酸海因)的结构(几何形状、电子结构)、振动光谱(红外)和光化学特征,以及取代基对这些性质的影响。研究结果表明,海因分子普遍倾向于平面性(或准平面性),这主要是由体系中的π电子析出决定的,其中两个氮原子广泛参与,在所研究的分子中,还与 -C5H2- 或 -C5HR-(在 5-甲基海因和 5-乙酸海因中,R ˭ CH3 或 CH2COOH 分别)片段的π型轨道参与有关(超共轭)。化合物的几何结构和电荷密度分析还表明,海因环中的主要电子效应是 N 对(C ˭ O)π 电子捐赠,以及氧原子的 σ 单电子对对环的 σ 系统反捐赠。比较讨论了在不同化合物的基质分离红外光谱(Ar;10 K)中观察到的归属于羰基和胺片段的条带频率,并评估了取代基的影响。最后,紫外线(λ = 320 纳米)诱导的海因光化学反应显示出一种共同的模式,即异氰酸和一氧化碳协同挤出,同时产生亚胺衍生物,这取决于特定的海因反应物。对于 1-甲基海因来说,还存在一个额外的光破碎途径,很可能涉及腈中间体,这表明海因环 1 位上的取代对海因的光破碎有特殊的影响。
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Revisiting structural, vibrational, and photochemical data of matrix-isolated simple hydantoins — Common features and substituent effects
Characteristic features of the structure (geometries, electronic structures), vibrational spectra (infrared), and photochemistry of a series of simple hydantoins (parent hydantoin, 1-methylhydantoin, 5-methylhydantoin, and 5-acetic acid hydantoin), and effects of substituent on these properties, are reviewed in a comparative comprehensive perspective taken as a basis the low-temperature matrix isolation infrared spectroscopy and electronic structure quantum chemistry data we have reported before for the individual compounds. It is shown that the hydantoin moiety shows a general tendency towards planarity (or quasi-planarity), mostly determined by the π-electron delocalization in the system, in which the two nitrogen atoms are extensively involved and, in the molecules studied, also counts with the involvement of the π-type orbitals of the –C5H2– or –C5HR– (with R ˭ CH3 or CH2COOH in 5-methylhydantoin and 5-acetic acid hydantoin, respectively) fragment (hyperconjugation). The geometries and charge density analyses of the compounds also show that the main electronic effects in the hydantoin ring are the N-to-(C ˭ O) π-electron donation, and the σ system back-donation from the σ-lone electron pairs of the oxygen atoms to the ring. The frequencies of the bands observed in the matrix-isolation infrared spectra (Ar; 10 K) of the different compounds that are assigned to the carbonyl and amine fragments are discussed comparatively, and substituent effects are assessed. Finally, the UV-induced (λ = 320 nm) photochemistry of the hydantoins is shown to share a common pattern, leading to the concerted extrusion of isocyanic acid and carbon monoxide, accompanied by an imine derivative that depends upon the specific hydantoin reactant. An additional photofragmentation pathway, most probably involving nitrene intermediacy, also takes place for 1-methylhydantoin, indicating a specific effect of the substitution at position 1 of the hydantoin ring on the photofragmentation of hydantoins.
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来源期刊
Low Temperature Physics
Low Temperature Physics 物理-物理:应用
CiteScore
1.20
自引率
25.00%
发文量
138
审稿时长
3 months
期刊介绍: Guided by an international editorial board, Low Temperature Physics (LTP) communicates the results of important experimental and theoretical studies conducted at low temperatures. LTP offers key work in such areas as superconductivity, magnetism, lattice dynamics, quantum liquids and crystals, cryocrystals, low-dimensional and disordered systems, electronic properties of normal metals and alloys, and critical phenomena. The journal publishes original articles on new experimental and theoretical results as well as review articles, brief communications, memoirs, and biographies. Low Temperature Physics, a translation of the copyrighted Journal FIZIKA NIZKIKH TEMPERATUR, is a monthly journal containing English reports of current research in the field of the low temperature physics. The translation began with the 1975 issues. One volume is published annually beginning with the January issues.
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