Steric Hindrance Effect as a Decisive Factor for the Self-Assembly of Metallocages,Inorganic Chemistry

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Steric Hindrance Effect as a Decisive Factor for the Self-Assembly of Metallocages
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2023-04-19 , DOI: 10.1021/acs.inorgchem.3c00026
Guotao Wang _{1,

2,

3} , Qixia Bai ₄ , Hui Liu _{1,

2,

3} , Zhengguang Li ₅ , Zhiyuan Jiang ₅ , Zhe Zhang ₄ , Yiming Li ₅ , Pingshan Wang _{2,

4,

5}

Affiliation

In the past decades, many supramolecular cages with different sizes and shapes have been achieved through coordination-driven self-assembly. However, the strategy of topology adjustment by using a steric hindrance effect has not been fully developed. In this Article, we report the synthesis of ligand LA with rotatable arms, ligand LB with restricted arms, and their precisely controlled self-assembly to tetramer cage T1 and dimer cage D1, respectively, under the same conditions. By utilizing the steric hindrance of the ligands, the shapes and sizes of metallosupramolecular cages have been successfully adjusted. The metallocages were characterized by NMR spectroscopy (¹H, ¹³C, COSY, NOESY, and DOSY), mass spectrometry (ESI-MS, TWIM-MS), transmission electron microscopy, and atomic force microscopy. This synthetic method would have the potential to be a general strategy for the design and self-assembly of diverse cages with tunable shape, size, and applicable properties.

中文翻译：

位阻效应作为金属笼自组装的决定性因素

在过去的几十年里，许多不同大小和形状的超分子笼已经通过配位驱动的自组装实现。然而，利用空间位阻效应调整拓扑结构的策略尚未得到充分开发。在这篇文章中，我们报道了具有旋转臂的配体LA和具有限制臂的配体LB的合成，以及它们在相同条件下分别精确控制的自组装到四聚体笼T1和二聚体笼D1 。利用配体的空间位阻，成功地调整了金属超分子笼的形状和大小。通过核磁共振光谱 ( ¹ H, ¹³C、COSY、NOESY 和 DOSY）、质谱（ESI-MS、TWIM-MS）、透射电子显微镜和原子力显微镜。这种合成方法有可能成为设计和自组装具有可调形状、尺寸和适用特性的各种笼子的通用策略。

更新日期：2023-04-19

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