A new supramolecular catalytic system: the self-assembly of Rh8 cage host anthracene molecules for [4 + 4] cycloaddition induced by UV irradiation.,Dalton Transactions

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A new supramolecular catalytic system: the self-assembly of Rh8 cage host anthracene molecules for [4 + 4] cycloaddition induced by UV irradiation.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-06-17 , DOI: 10.1039/d0dt01978j
Wei-Bin Yu ₁ , Feng-Yi Qiu , Po Sun , Hua-Tian Shi , Zhi-Feng Xin

Affiliation

The supramolecular assembly, used as a molecular reactor, is of great significance in host–guest chemistry. In this work, we used a tetratopic pyridyl ligand as a building block to hierarchically combine a slightly twisted cuboid with half-sandwich rhodium fragments. The cuboid directionally self-assembled hydrophobic pockets that can encapsulate conjugated molecules like anthracene (ANT) as guests in solutions, by supramolecular interactions including hydrogen bonding and hydrophobic interactions. The array of the ANT molecules in the confined pockets was subjected to a [4 + 4] photocycloaddition reaction under UV light irradiation as an external stimulus in a methanol solution. Furthermore, the mechanism underlying the process was proposed. The cuboid was fully characterized by ¹H NMR, single-crystal X-ray diffraction (SCXRD), and mass spectrometry (MS), and its host–guest and cycloaddition processes were monitored by ¹H NMR spectroscopy and UV-visible spectrophotometry.

中文翻译：

一种新的超分子催化系统：Rh8笼宿主蒽分子的自组装，用于紫外线照射诱导的[4 + 4]环加成。

用作分子反应器的超分子组装在客体-客体化学中具有重要意义。在这项工作中，我们使用四位吡啶基配位体作为构建基，将略微扭曲的长方体与半夹心铑片段分层地组合在一起。立方定向自组装疏水袋，可通过超分子相互作用（包括氢键和疏水相互作用）将诸如蒽（ANT）等共轭分子封装为溶液。在甲醇溶液中，作为外部刺激，在紫外线照射下，将受限囊中的ANT分子阵列进行[4 + 4]光环加成反应。此外，提出了该过程的基础机制。长方体的特征在于¹¹ H NMR光谱和UV-可见分光光度法监测¹ H NMR，单晶X射线衍射（SCXRD）和质谱（MS）以及其主客体和环加成过程。

更新日期：2020-07-21

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