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

Guotao Wang; Qixia Bai; Hui Liu; Zhengguang Li; Zhiyuan Jiang; Zhe Zhang; Yiming Li; Pingshan Wang

doi:10.1021/acs.inorgchem.3c00026

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

Inorg Chem. 2023 May 1;62(17):6537-6543. doi: 10.1021/acs.inorgchem.3c00026. Epub 2023 Apr 19.

Authors

Guotao Wang^{1

2

3}, Qixia Bai⁴, Hui Liu^{1

2

3}, Zhengguang Li⁵, Zhiyuan Jiang⁵, Zhe Zhang⁴, Yiming Li⁵, Pingshan Wang^{5

4

2}

Affiliations

¹ School of Metallurgy and Environment, Central South University, Changsha, Hunan 410083, China.
² Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, Changsha, Hunan 410083, China.
³ State Key Laboratory of Advanced Metallurgy for Non-ferrous Metals, Changsha, Hunan 410083, China.
⁴ Institute of Environmental Research at Greater Bay Area, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, and Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, China.
⁵ Department of Organic and Polymer Chemistry and Hunan Key Laboratory of Micro and Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China.

PMID: 37074131
DOI: 10.1021/acs.inorgchem.3c00026

Abstract

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.