宿主空腔和八乙酸诱导的取向异构对环己烯光氧化反应产物选择性的影响

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-05-05 DOI:10.1016/j.jphotochem.2025.116481

Shipra Gupta , V. Ramamurthy

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引用次数: 0

摘要

“取向同分异构”是深入理解主客体体系中选择性反应的必要概念。这个概念很少在超分子主客体化学的背景下进行探索。我们设计了一个模型体系，包括四个环己烯衍生物和一个水溶性的八羧酸（OA），具有疏水的内腔。客体分子的总长度（~ 12 Å）通过控制环己烯环上1位和4位的烷基取代基而受到限制。利用1D 1H/2D COSY和NOESY NMR和光氧化反应来了解该模型系统的观测结果。由宿主OA诱导的每个客体分子的特异性包装或“取向异构体”导致特异性的，在一种情况下增强了产品的选择性。通过这个模型系统，我们展示了“取向异构”在解释主客体超分子体系中增强的产物选择性方面的重要作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Product selectivity in photo-oxygenation reaction of cyclohexenes due to orientational isomerism induced by host cavitand Octa Acid

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Product selectivity in photo-oxygenation reaction of cyclohexenes due to orientational isomerism induced by host cavitand Octa Acid

“Orientational isomerism” is a concept necessary for deeper understanding of the selective reactivities in a host–guest system. This concept has been rarely explored in the context of supramolecular host guest chemistry. We designed a model system including four cyclohexene derivatives and a water-soluble host Octa Acid (OA), with hydrophobic inner cavity. The overall length of the guest molecules (∼12 Å) was limited by manipulating the alkyl substituents at 1- and 4-positions on the cyclohexene ring. 1D ¹H/2D COSY and NOESY NMR and photo-oxygenation reaction were used to understand the observations with this model system. Specific packaging or “orientational isomerism” of each guest molecule, induced by the host OA led to specific, in one case enhanced product selectivity. With this model system we show the important role of “orientational isomerism” in explaining enhanced product selectivity in a host–guest supramolecular system.

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来源期刊

Journal of Photochemistry and Photobiology A-chemistry 化学-物理化学

CiteScore

7.90

自引率

7.00%

发文量

580

审稿时长

48 days

期刊介绍： JPPA publishes the results of fundamental studies on all aspects of chemical phenomena induced by interactions between light and molecules/matter of all kinds. All systems capable of being described at the molecular or integrated multimolecular level are appropriate for the journal. This includes all molecular chemical species as well as biomolecular, supramolecular, polymer and other macromolecular systems, as well as solid state photochemistry. In addition, the journal publishes studies of semiconductor and other photoactive organic and inorganic materials, photocatalysis (organic, inorganic, supramolecular and superconductor). The scope includes condensed and gas phase photochemistry, as well as synchrotron radiation chemistry. A broad range of processes and techniques in photochemistry are covered such as light induced energy, electron and proton transfer; nonlinear photochemical behavior; mechanistic investigation of photochemical reactions and identification of the products of photochemical reactions; quantum yield determinations and measurements of rate constants for primary and secondary photochemical processes; steady-state and time-resolved emission, ultrafast spectroscopic methods, single molecule spectroscopy, time resolved X-ray diffraction, luminescence microscopy, and scattering spectroscopy applied to photochemistry. Papers in emerging and applied areas such as luminescent sensors, electroluminescence, solar energy conversion, atmospheric photochemistry, environmental remediation, and related photocatalytic chemistry are also welcome.