Issue 4, 2021

Facile construction of well-defined radical metallacycles through coordination-driven self-assembly

Abstract

Recently, the marriage of organic radicals and supramolecular chemistry has given birth to a booming research field of supramolecular radical chemistry. However, the well-developed supramolecular radical systems are still limited, especially at present the supramolecular coordination radical systems are rarely explored. The construction of discrete supramolecular radical coordination complexes such as radical metallacycles and metallacages still remains a great challenge mainly because of the intrinsically unstable nature of organic radicals and the lack of suitable coordination method. Herein, we design and synthesize a new organic radical ligand CzBTM-Py with well-defined coordination geometry and persistent stability. Subsequently, two discrete radical metallacycles of M1 and M2 are successfully and efficiently constructed via the coordination-driven self-assembly approach. Due to the mild coordination reaction conditions the open-shell nature of CzBTM-Py is preserved as indicated by the electron paramagnetic resonance (EPR) spectroscopy. The chemical structures of CzBTM-Py, M1 and M2 are successfully determined by X-ray crystallography. Interestingly, a chiral self-sorting behavior is observed in this coordination-driven self-assembly process, i.e., M1 exists as MM/PP enantiomers couple while M2 exists as the heterochiral PM form. Moreover, the photophysical properties of the radicals have changed significantly after coordination, making the color and emission of M1 and M2 differ from those of CzBTM-Py. Additionally, metallacycles M1 and M2 show better photostability than radical ligand CzBTM-Py. This work successfully demonstrates a highly efficient coordination-driven self-assembly approach to synthesize radical-based supramolecular coordination complexes, which could modulate the chemical and physical properties of organic radicals, and thus to develop new functional metal–organic radical materials.

Graphical abstract: Facile construction of well-defined radical metallacycles through coordination-driven self-assembly

Supplementary files

Article information

Article type
Research Article
Submitted
27 noy 2020
Accepted
08 yan 2021
First published
12 yan 2021

Mater. Chem. Front., 2021,5, 1863-1871

Facile construction of well-defined radical metallacycles through coordination-driven self-assembly

Q. Tu, G. Huo, X. Zhao, H. Sun, X. Shi and H. Yang, Mater. Chem. Front., 2021, 5, 1863 DOI: 10.1039/D0QM00992J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements