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Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length

Yim, King-Him; Yeung, Chi-Tung; Probert, Michael R.; Chan, Wesley Ting Kwok; MacKenzie, Lewis E.; Pal, Robert; Wong, Wing-Tak; Law, Ga-Lai

Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length Thumbnail


Authors

King-Him Yim

Chi-Tung Yeung

Michael R. Probert

Wesley Ting Kwok Chan

Lewis E. MacKenzie

Wing-Tak Wong

Ga-Lai Law



Abstract

Controlled formation of desired lanthanide supramolecular complexes is challenging because of the difficulties in predicting coordination geometry, as well as a labile coordination number. Herein, we explore the effect of ionic radii and linker length on supramolecular species formation. A helicate-to-tetrahedron transformation occurred between [Ln2L13] and [Ln4L16] (Ln = La, Sm, Eu, Gd, Tb and Lu). For six lanthanide ions, the unfavored tetrahedron [La4L16] can only be observed in a concentrated mixture with the helicate [La2L13] where no pure [La4L16] species was isolated via crystallization. For Sm, Eu, Gd, Tb, the [Ln4L16] supramolecular tetrahedron can be isolated via crystallization from diisopropyl ether. A similar result was also observed for Lu, but the tetrahedral structure was found to be relatively stable and transformed back to [Lu2L13] much slower upon dissolution. No tetrahedron formation was observed with L3 giving rise to only [Ln2L33] species, in which L3 contains a longer and more flexible linker compared with that of L1. Results show that the supramolecular transformation in these systems is governed by both the ionic radii as well as the ligand design. Special focus is on both [Eu2L13] and [Eu4L16] which form chiral entities and exhibit interesting circular polarized luminescence.

Citation

Yim, K., Yeung, C., Probert, M. R., Chan, W. T. K., MacKenzie, L. E., Pal, R., …Law, G. (2021). Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length. Communications Chemistry, 4, Article 116. https://doi.org/10.1038/s42004-021-00553-8

Journal Article Type Article
Acceptance Date Jul 20, 2021
Online Publication Date Aug 5, 2021
Publication Date 2021
Deposit Date Aug 11, 2021
Publicly Available Date Dec 17, 2021
Journal Communications Chemistry
Publisher Nature Research
Peer Reviewed Peer Reviewed
Volume 4
Article Number 116
DOI https://doi.org/10.1038/s42004-021-00553-8

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http://creativecommons.org/licenses/by/4.0/

Copyright Statement
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.





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