Cargando…
Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets
Luminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloli...
Autores principales: | , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2021
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8166919/ https://www.ncbi.nlm.nih.gov/pubmed/34059691 http://dx.doi.org/10.1038/s41598-021-88446-7 |
_version_ | 1783701596286222336 |
---|---|
author | Wegner, Wojciech Zakrzewski, Jakub J. Zychowicz, Mikolaj Chorazy, Szymon |
author_facet | Wegner, Wojciech Zakrzewski, Jakub J. Zychowicz, Mikolaj Chorazy, Szymon |
author_sort | Wegner, Wojciech |
collection | PubMed |
description | Luminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloligands. We present a simple route to luminescent SMMs realized by the insertion of well-known organic cations, tetrabutylammonium and tetraphenylphosphonium, into dysprosium(III) borohydrides, the representatives of metal borohydrides investigated due to their hydrogen storage properties. We report two novel compounds, [n-Bu(4)N][Dy(III)(BH(4))(4)] (1) and [Ph(4)P][Dy(III)(BH(4))(4)] (2), involving Dy(III) centers surrounded by four pseudo-tetrahedrally arranged BH(4)(–) ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I4(1)/a), 1 crystallizes in a less symmetric monoclinic unit cell (P2(1)/c). They exhibit yellow room-temperature photoluminescence related to the f–f electronic transitions. Moreover, they reveal Dy(III)-centered magnetic anisotropy generated by the distorted arrangement of four borohydride anions. It leads to field-induced slow magnetic relaxation, well-observed for the magnetically diluted samples, [n-Bu(4)N][Y(III)(0.9)Dy(III)(0.1)(BH(4))(4)] (1@Y) and [Ph(4)P][Y(III)(0.9)Dy(III)(0.1)(BH(4))(4)] (2@Y). 1@Y exhibits an Orbach-type relaxation with an energy barrier of 26.4(5) K while only the onset of SMM features was found in 2@Y. The more pronounced single-ion anisotropy of Dy(III) complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1–2 and the highly symmetrical inorganic Dy(III) borohydrides, α/β-Dy(BH(4))(3), 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of Dy(III) centers inducing single-ion anisotropy and separate them in the crystal lattice enabling the emission property. These findings are supported by the comparison with 3 and 4, crystalizing in cubic unit cells, which are not emissive and do not exhibit SMM behavior. |
format | Online Article Text |
id | pubmed-8166919 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-81669192021-06-02 Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets Wegner, Wojciech Zakrzewski, Jakub J. Zychowicz, Mikolaj Chorazy, Szymon Sci Rep Article Luminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloligands. We present a simple route to luminescent SMMs realized by the insertion of well-known organic cations, tetrabutylammonium and tetraphenylphosphonium, into dysprosium(III) borohydrides, the representatives of metal borohydrides investigated due to their hydrogen storage properties. We report two novel compounds, [n-Bu(4)N][Dy(III)(BH(4))(4)] (1) and [Ph(4)P][Dy(III)(BH(4))(4)] (2), involving Dy(III) centers surrounded by four pseudo-tetrahedrally arranged BH(4)(–) ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I4(1)/a), 1 crystallizes in a less symmetric monoclinic unit cell (P2(1)/c). They exhibit yellow room-temperature photoluminescence related to the f–f electronic transitions. Moreover, they reveal Dy(III)-centered magnetic anisotropy generated by the distorted arrangement of four borohydride anions. It leads to field-induced slow magnetic relaxation, well-observed for the magnetically diluted samples, [n-Bu(4)N][Y(III)(0.9)Dy(III)(0.1)(BH(4))(4)] (1@Y) and [Ph(4)P][Y(III)(0.9)Dy(III)(0.1)(BH(4))(4)] (2@Y). 1@Y exhibits an Orbach-type relaxation with an energy barrier of 26.4(5) K while only the onset of SMM features was found in 2@Y. The more pronounced single-ion anisotropy of Dy(III) complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1–2 and the highly symmetrical inorganic Dy(III) borohydrides, α/β-Dy(BH(4))(3), 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of Dy(III) centers inducing single-ion anisotropy and separate them in the crystal lattice enabling the emission property. These findings are supported by the comparison with 3 and 4, crystalizing in cubic unit cells, which are not emissive and do not exhibit SMM behavior. Nature Publishing Group UK 2021-05-31 /pmc/articles/PMC8166919/ /pubmed/34059691 http://dx.doi.org/10.1038/s41598-021-88446-7 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 licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence 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 licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Wegner, Wojciech Zakrzewski, Jakub J. Zychowicz, Mikolaj Chorazy, Szymon Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets |
title | Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets |
title_full | Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets |
title_fullStr | Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets |
title_full_unstemmed | Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets |
title_short | Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets |
title_sort | incorporation of expanded organic cations in dysprosium(iii) borohydrides for achieving luminescent molecular nanomagnets |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8166919/ https://www.ncbi.nlm.nih.gov/pubmed/34059691 http://dx.doi.org/10.1038/s41598-021-88446-7 |
work_keys_str_mv | AT wegnerwojciech incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets AT zakrzewskijakubj incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets AT zychowiczmikolaj incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets AT chorazyszymon incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets |