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Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods
During the last few years, a large number of mononuclear Co(ii) complexes of various coordination geometries have been explored as potential single ion magnets (SIMs). In the work presented herein, the Co(ii) S = 3/2 tetrahedral [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, complexes (abbreviated as CoO(...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9926333/ https://www.ncbi.nlm.nih.gov/pubmed/36692040 http://dx.doi.org/10.1039/d2dt03335f |
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author | Ferentinos, Eleftherios Tzeli, Demeter Sottini, Silvia Groenen, Edgar J. J. Ozerov, Mykhaylo Poneti, Giordano Kaniewska-Laskowska, Kinga Krzystek, J. Kyritsis, Panayotis |
author_facet | Ferentinos, Eleftherios Tzeli, Demeter Sottini, Silvia Groenen, Edgar J. J. Ozerov, Mykhaylo Poneti, Giordano Kaniewska-Laskowska, Kinga Krzystek, J. Kyritsis, Panayotis |
author_sort | Ferentinos, Eleftherios |
collection | PubMed |
description | During the last few years, a large number of mononuclear Co(ii) complexes of various coordination geometries have been explored as potential single ion magnets (SIMs). In the work presented herein, the Co(ii) S = 3/2 tetrahedral [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, complexes (abbreviated as CoO(2)E(2)), bearing chalcogenated mixed donor-atom imidodiphosphinato ligands, were studied by both experimental and computational techniques. Specifically, direct current (DC) magnetometry provided estimations of their zero-field splitting (zfs) axial (D) and rhombic (E) parameter values, which were more accurately determined by a combination of far-infrared magnetic spectroscopy and high-frequency and -field EPR spectroscopy studies. The latter combination of techniques was also implemented for the S = 3/2 tetrahedral [Co{(EP(i)Pr(2))(2)N}(2)], E = S, Se, complexes, confirming the previously determined magnitude of their zfs parameters. For both pairs of complexes (E = S, Se), it is concluded that the identity of the E donor atom does not significantly affect their zfs parameters. High-resolution multifrequency EPR studies of CoO(2)E(2) provided evidence of multiple conformations, which are more clearly observed for CoO(2)Se(2), in agreement with the structural disorder previously established for this complex by X-ray crystallography. The CoO(2)E(2) complexes were shown to be field-induced SIMs, i.e., they exhibit slow relaxation of magnetization in the presence of an external DC magnetic field. Advanced quantum-chemical calculations on CoO(2)E(2) provided additional insight into their electronic and structural properties. |
format | Online Article Text |
id | pubmed-9926333 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-99263332023-02-15 Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods Ferentinos, Eleftherios Tzeli, Demeter Sottini, Silvia Groenen, Edgar J. J. Ozerov, Mykhaylo Poneti, Giordano Kaniewska-Laskowska, Kinga Krzystek, J. Kyritsis, Panayotis Dalton Trans Chemistry During the last few years, a large number of mononuclear Co(ii) complexes of various coordination geometries have been explored as potential single ion magnets (SIMs). In the work presented herein, the Co(ii) S = 3/2 tetrahedral [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, complexes (abbreviated as CoO(2)E(2)), bearing chalcogenated mixed donor-atom imidodiphosphinato ligands, were studied by both experimental and computational techniques. Specifically, direct current (DC) magnetometry provided estimations of their zero-field splitting (zfs) axial (D) and rhombic (E) parameter values, which were more accurately determined by a combination of far-infrared magnetic spectroscopy and high-frequency and -field EPR spectroscopy studies. The latter combination of techniques was also implemented for the S = 3/2 tetrahedral [Co{(EP(i)Pr(2))(2)N}(2)], E = S, Se, complexes, confirming the previously determined magnitude of their zfs parameters. For both pairs of complexes (E = S, Se), it is concluded that the identity of the E donor atom does not significantly affect their zfs parameters. High-resolution multifrequency EPR studies of CoO(2)E(2) provided evidence of multiple conformations, which are more clearly observed for CoO(2)Se(2), in agreement with the structural disorder previously established for this complex by X-ray crystallography. The CoO(2)E(2) complexes were shown to be field-induced SIMs, i.e., they exhibit slow relaxation of magnetization in the presence of an external DC magnetic field. Advanced quantum-chemical calculations on CoO(2)E(2) provided additional insight into their electronic and structural properties. The Royal Society of Chemistry 2023-01-24 /pmc/articles/PMC9926333/ /pubmed/36692040 http://dx.doi.org/10.1039/d2dt03335f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Ferentinos, Eleftherios Tzeli, Demeter Sottini, Silvia Groenen, Edgar J. J. Ozerov, Mykhaylo Poneti, Giordano Kaniewska-Laskowska, Kinga Krzystek, J. Kyritsis, Panayotis Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods |
title | Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods |
title_full | Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods |
title_fullStr | Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods |
title_full_unstemmed | Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods |
title_short | Magnetic anisotropy and structural flexibility in the field-induced single ion magnets [Co{(OPPh(2))(EPPh(2))N}(2)], E = S, Se, explored by experimental and computational methods |
title_sort | magnetic anisotropy and structural flexibility in the field-induced single ion magnets [co{(opph(2))(epph(2))n}(2)], e = s, se, explored by experimental and computational methods |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9926333/ https://www.ncbi.nlm.nih.gov/pubmed/36692040 http://dx.doi.org/10.1039/d2dt03335f |
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