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Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes

[Image: see text] The reaction of fluoride anions with mononuclear lanthanide(III) and yttrium(III) hexaaza-macrocyclic complexes results in the formation of dinuclear fluoride-bridged complexes. As indicated by X-ray crystal structures, in these complexes two metal ions bound by the macrocycles are...

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Autores principales: Ślepokura, Katarzyna, Cabreros, Trevor A., Muller, Gilles, Lisowski, Jerzy
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8653217/
https://www.ncbi.nlm.nih.gov/pubmed/34784708
http://dx.doi.org/10.1021/acs.inorgchem.1c03034
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author Ślepokura, Katarzyna
Cabreros, Trevor A.
Muller, Gilles
Lisowski, Jerzy
author_facet Ślepokura, Katarzyna
Cabreros, Trevor A.
Muller, Gilles
Lisowski, Jerzy
author_sort Ślepokura, Katarzyna
collection PubMed
description [Image: see text] The reaction of fluoride anions with mononuclear lanthanide(III) and yttrium(III) hexaaza-macrocyclic complexes results in the formation of dinuclear fluoride-bridged complexes. As indicated by X-ray crystal structures, in these complexes two metal ions bound by the macrocycles are linked by two or three bridging fluoride anions, depending on the type of the macrocycle. In the case of the chiral hexaaza-macrocycle L1 derived from trans-1,2-diaminocyclohexane, the formation of these μ(2)-fluorido dinuclear complexes is accompanied by enantiomeric self-recognition of macrocyclic units. In contrast, this kind of recognition is not observed in the case of complexes of the chiral macrocycle L2 derived from 1,2-diphenylethylenediamine. The reaction of fluoride with a mixture of mononuclear complexes of L1 and L2, containing two different Ln(III) ions, results in narcissistic sorting of macrocyclic units. Conversely, a similar reaction involving mononuclear complexes of L1 and complexes of achiral macrocycle L3 based on ethylenediamine results in sociable sorting of macrocyclic units and preferable formation of heterodinuclear complexes. In addition, formation of these heterodinuclear complexes is accompanied by chirality transfer from the chiral macrocycle L1 to the achiral macrocycle L3 as indicated by CPL and CD spectra.
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spelling pubmed-86532172021-12-09 Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes Ślepokura, Katarzyna Cabreros, Trevor A. Muller, Gilles Lisowski, Jerzy Inorg Chem [Image: see text] The reaction of fluoride anions with mononuclear lanthanide(III) and yttrium(III) hexaaza-macrocyclic complexes results in the formation of dinuclear fluoride-bridged complexes. As indicated by X-ray crystal structures, in these complexes two metal ions bound by the macrocycles are linked by two or three bridging fluoride anions, depending on the type of the macrocycle. In the case of the chiral hexaaza-macrocycle L1 derived from trans-1,2-diaminocyclohexane, the formation of these μ(2)-fluorido dinuclear complexes is accompanied by enantiomeric self-recognition of macrocyclic units. In contrast, this kind of recognition is not observed in the case of complexes of the chiral macrocycle L2 derived from 1,2-diphenylethylenediamine. The reaction of fluoride with a mixture of mononuclear complexes of L1 and L2, containing two different Ln(III) ions, results in narcissistic sorting of macrocyclic units. Conversely, a similar reaction involving mononuclear complexes of L1 and complexes of achiral macrocycle L3 based on ethylenediamine results in sociable sorting of macrocyclic units and preferable formation of heterodinuclear complexes. In addition, formation of these heterodinuclear complexes is accompanied by chirality transfer from the chiral macrocycle L1 to the achiral macrocycle L3 as indicated by CPL and CD spectra. American Chemical Society 2021-11-16 2021-12-06 /pmc/articles/PMC8653217/ /pubmed/34784708 http://dx.doi.org/10.1021/acs.inorgchem.1c03034 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Ślepokura, Katarzyna
Cabreros, Trevor A.
Muller, Gilles
Lisowski, Jerzy
Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes
title Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes
title_full Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes
title_fullStr Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes
title_full_unstemmed Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes
title_short Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes
title_sort sorting phenomena and chirality transfer in fluoride-bridged macrocyclic rare earth complexes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8653217/
https://www.ncbi.nlm.nih.gov/pubmed/34784708
http://dx.doi.org/10.1021/acs.inorgchem.1c03034
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