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From the {Fe(III) (2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters
In this Review we discuss the tuning handles which can be used to steer the magnetic properties of Fe(III)‐4 f “butterfly” compounds. The majority of presented compounds were produced in the context of project A3 “Di‐ to tetranuclear compounds incorporating highly anisotropic paramagnetic metal ions...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8597143/ https://www.ncbi.nlm.nih.gov/pubmed/34582064 http://dx.doi.org/10.1002/chem.202102962 |
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author | Peng, Yan Kaemmerer, Hagen Powell, Annie K. |
author_facet | Peng, Yan Kaemmerer, Hagen Powell, Annie K. |
author_sort | Peng, Yan |
collection | PubMed |
description | In this Review we discuss the tuning handles which can be used to steer the magnetic properties of Fe(III)‐4 f “butterfly” compounds. The majority of presented compounds were produced in the context of project A3 “Di‐ to tetranuclear compounds incorporating highly anisotropic paramagnetic metal ions” within the SFB/TRR88 “3MET”. These contain {Fe(III) (2)Ln(2)} cores encapsulated in ligand shells which are easy to tune in a “test‐bed” system. We identify the following advantages and variables in such systems: (i) the complexes are structurally simple usually with one crystallographically independent Fe(III) and Ln(III), respectively. This simplifies theory and anaylsis; (ii) choosing Fe allows (57)Fe Mössbauer spectroscopy to be used as an additional technique which can give information about oxidation levels and spin states, local moments at the iron nuclei and spin‐relaxation and, more importantly, about the anisotropy not only of the studied isotope, but also of elements interacting with this isotope; (iii) isostructural analogues with all the available (i. e. not Pm) 4 f ions can be synthesised, enabling a systematic survey of the influence of the 4 f ion on the electronic structure; (iv) this cluster type is obtained by reacting [Fe(III) (3)O(O(2)CR)(6)(L)(3)](X) (X=anion, L=solvent such as H(2)O, py) with an ethanolamine‐based ligand L′ and lanthanide salts. This allows to study analogues of [Fe(III) (2)Ln(2)(μ(3)‐OH)(2)(L′)(2)(O(2)CR)(6)] using the appropriate iron trinuclear starting materials. (v) the organic main ligand can be readily functionalised, facilitating a systematic investigation of the effect of organic substituents on the ligands on the magnetic properties of the complexes. We describe and discuss 34 {M(III) (2)Ln(2)} (M=Fe or in one case Al) butterfly compounds which have been reported up to 2020. The analysis of these gives perspectives for designing new SMM systems with specific electronic and magnetic signatures |
format | Online Article Text |
id | pubmed-8597143 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-85971432021-11-22 From the {Fe(III) (2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters Peng, Yan Kaemmerer, Hagen Powell, Annie K. Chemistry Reviews In this Review we discuss the tuning handles which can be used to steer the magnetic properties of Fe(III)‐4 f “butterfly” compounds. The majority of presented compounds were produced in the context of project A3 “Di‐ to tetranuclear compounds incorporating highly anisotropic paramagnetic metal ions” within the SFB/TRR88 “3MET”. These contain {Fe(III) (2)Ln(2)} cores encapsulated in ligand shells which are easy to tune in a “test‐bed” system. We identify the following advantages and variables in such systems: (i) the complexes are structurally simple usually with one crystallographically independent Fe(III) and Ln(III), respectively. This simplifies theory and anaylsis; (ii) choosing Fe allows (57)Fe Mössbauer spectroscopy to be used as an additional technique which can give information about oxidation levels and spin states, local moments at the iron nuclei and spin‐relaxation and, more importantly, about the anisotropy not only of the studied isotope, but also of elements interacting with this isotope; (iii) isostructural analogues with all the available (i. e. not Pm) 4 f ions can be synthesised, enabling a systematic survey of the influence of the 4 f ion on the electronic structure; (iv) this cluster type is obtained by reacting [Fe(III) (3)O(O(2)CR)(6)(L)(3)](X) (X=anion, L=solvent such as H(2)O, py) with an ethanolamine‐based ligand L′ and lanthanide salts. This allows to study analogues of [Fe(III) (2)Ln(2)(μ(3)‐OH)(2)(L′)(2)(O(2)CR)(6)] using the appropriate iron trinuclear starting materials. (v) the organic main ligand can be readily functionalised, facilitating a systematic investigation of the effect of organic substituents on the ligands on the magnetic properties of the complexes. We describe and discuss 34 {M(III) (2)Ln(2)} (M=Fe or in one case Al) butterfly compounds which have been reported up to 2020. The analysis of these gives perspectives for designing new SMM systems with specific electronic and magnetic signatures John Wiley and Sons Inc. 2021-10-19 2021-11-02 /pmc/articles/PMC8597143/ /pubmed/34582064 http://dx.doi.org/10.1002/chem.202102962 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Reviews Peng, Yan Kaemmerer, Hagen Powell, Annie K. From the {Fe(III) (2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters |
title | From the {Fe(III)
(2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters |
title_full | From the {Fe(III)
(2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters |
title_fullStr | From the {Fe(III)
(2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters |
title_full_unstemmed | From the {Fe(III)
(2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters |
title_short | From the {Fe(III)
(2)Ln(2)} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters |
title_sort | from the {fe(iii)
(2)ln(2)} butterfly's perspective: the magnetic benefits and challenges of cooperativity within 3 d–4 f based coordination clusters |
topic | Reviews |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8597143/ https://www.ncbi.nlm.nih.gov/pubmed/34582064 http://dx.doi.org/10.1002/chem.202102962 |
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