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

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-...

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Autores principales: Yim, King-Him, Yeung, Chi-Tung, Probert, Michael R., Chan, Wesley Ting Kwok, Mackenzie, Lewis E., Pal, Robert, Wong, Wing-Tak, Law, Ga-Lai
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814731/
https://www.ncbi.nlm.nih.gov/pubmed/36697590
http://dx.doi.org/10.1038/s42004-021-00553-8
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author Yim, King-Him
Yeung, Chi-Tung
Probert, Michael R.
Chan, Wesley Ting Kwok
Mackenzie, Lewis E.
Pal, Robert
Wong, Wing-Tak
Law, Ga-Lai
author_facet Yim, King-Him
Yeung, Chi-Tung
Probert, Michael R.
Chan, Wesley Ting Kwok
Mackenzie, Lewis E.
Pal, Robert
Wong, Wing-Tak
Law, Ga-Lai
author_sort Yim, King-Him
collection PubMed
description 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 [Ln(2)L1(3)] and [Ln(4)L1(6)] (Ln = La, Sm, Eu, Gd, Tb and Lu). For six lanthanide ions, the unfavored tetrahedron [La(4)L1(6)] can only be observed in a concentrated mixture with the helicate [La(2)L1(3)] where no pure [La(4)L1(6)] species was isolated via crystallization. For Sm, Eu, Gd, Tb, the [Ln(4)L1(6)] 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 [Lu(2)L1(3)] much slower upon dissolution.  No tetrahedron formation was observed with L3 giving rise to only [Ln(2)L3(3)] 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 [Eu(2)L1(3)] and [Eu(4)L1(6)] which form chiral entities and exhibit interesting circular polarized luminescence.
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spelling pubmed-98147312023-01-10 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 Commun Chem Article 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 [Ln(2)L1(3)] and [Ln(4)L1(6)] (Ln = La, Sm, Eu, Gd, Tb and Lu). For six lanthanide ions, the unfavored tetrahedron [La(4)L1(6)] can only be observed in a concentrated mixture with the helicate [La(2)L1(3)] where no pure [La(4)L1(6)] species was isolated via crystallization. For Sm, Eu, Gd, Tb, the [Ln(4)L1(6)] 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 [Lu(2)L1(3)] much slower upon dissolution.  No tetrahedron formation was observed with L3 giving rise to only [Ln(2)L3(3)] 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 [Eu(2)L1(3)] and [Eu(4)L1(6)] which form chiral entities and exhibit interesting circular polarized luminescence. Nature Publishing Group UK 2021-08-05 /pmc/articles/PMC9814731/ /pubmed/36697590 http://dx.doi.org/10.1038/s42004-021-00553-8 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/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/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
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
title Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length
title_full Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length
title_fullStr Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length
title_full_unstemmed Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length
title_short Helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length
title_sort helicate-to-tetrahedron transformation of chiral lanthanide supramolecular complexes induced by ionic radii effect and linker length
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814731/
https://www.ncbi.nlm.nih.gov/pubmed/36697590
http://dx.doi.org/10.1038/s42004-021-00553-8
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