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Title: Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length
Authors: Yim, KH 
Yeung, CT 
Probert, MR
Chan, WTK 
Mackenzie, LE
Pal, R
Wong, WT 
Law, GL 
Issue Date: 2021
Source: Communications chemistry, 2021, v. 4, 116
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.
Publisher: Nature Publishing Group
Journal: Communications chemistry 
EISSN: 2399-3669
DOI: 10.1038/s42004-021-00553-8
Rights: © The Author(s) 2021
Open Access This article is licensed under a Creative CommonsAttribution 4.0 International License, which permits use, sharing,adaptation, distribution and reproduction in any medium or format, as long as you giveappropriate credit to the original author(s) and the source, provide a link to the CreativeCommons license, and indicate if changes were made. The images or other third partymaterial in this article are included in the article’s Creative Commons license, unlessindicated otherwise in a credit line to the material. If material is not included in thearticle’s Creative Commons license and your intended use is not permitted by statutoryregulation or exceeds the permitted use, you will need to obtain permission directly fromthe copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
The following publication Yim, KH., Yeung, CT., Probert, M.R. et al. Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length. Commun Chem 4, 116 (2021) is available at https://doi.org/10.1038/s42004-021-00553-8
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