关于包含三个苯亚单位的 [13] 至 [33] 双链环烷的构象和芳香性的理论研究

IF 2.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Structural Chemistry Pub Date : 2024-05-30 DOI:10.1007/s11224-024-02347-9
Mahsa Afshari, Hossein Fallah-Bagher-Shaidaei, Mohammad Nikpassand
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引用次数: 0

摘要

本研究在密度泛函理论的 B3LYP 水平上研究了 17 个 [13]、[23] 和 [33] 由三个苯分子组成的双链环烷的构象和芳香性。这些构象的稳定性因 (CH2) n 桥和外围苯环形成的环烷循环类型以及后者的曲率而不同。在 [13] 环烷中,这导致只有一种构象含有皱缩的环烷样循环,角度约为 37◦。相比之下,在环烷 [23] 和 [33] 中,相应的循环分别是环己烷状和环辛烷状。具有 TB 样循环的构象 2a 是 [23] 家族中最稳定的成员,而在 [33] 得到的八个基态构象中,具有两个椅状和一个捻椅状循环的 3a 是最稳定的构象,而具有三个捻船状循环的 3h 是该系列中最不稳定的成员,其能量比前者高 6.5 kcal。除了构象分析外,还使用了不同的指标来评估该系列的芳香性,包括笼和环中心的磁性标准核无关化学位移(NICS-based)、HNMR 化学位移、磁感应强度、HOMA 和相对能量(RE)。
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Theoretical study on the conformation and aromaticity of [13] to [33] double-stranded cyclophanes encompassing three benzene subunits

In the present study, conformations and aromaticity of seventeen [13], [23] and [33] double-stranded cyclophanes composed of three benzene moieties were investigated at B3LYP level of density functional theory. The stability of these conformers is different depending on the type of cycloalkane-like cycles formed by (CH2) n bridges and the peripheral benzene rings, and also the curvature of the latter. In [13] cyclophane, this leads to only one conformer containing puckered cyclobutane-like cycle, at an angle of about 37. In comparison, in cyclophanes [23] and [33], the corresponding cycles are cyclohexane-like and cyclooctane-like, respectively. While conformer 2a having TB-like cycles is the most stable member of the [23] family, of eight ground-state conformers obtained for [33], 3a with two Chair-Chair-like and one Twist-Chair-like cycles is the most stable one, and 3h with three Twist-Boat-like cycles being 6.5 kcal higher in energy than the former is the least stable member of series. In addition to the conformational analysis, the aromaticity of the series has been assessed using different indexes, including magnetic criteria nucleus-independent chemical shifts (NICS-based) at the cage and at the ring centers, HNMR chemical shift, Magnetic Susceptibility, HOMA and relative energy (RE).

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来源期刊
Structural Chemistry
Structural Chemistry 化学-化学综合
CiteScore
3.80
自引率
11.80%
发文量
227
审稿时长
3.7 months
期刊介绍: Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.
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