Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

Abstract 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...

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Autores principales:	Wojciech Wegner, Jakub J. Zakrzewski, Mikolaj Zychowicz, Szymon Chorazy
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/28ea0aa900874ae1b47854de5fbcc3c0
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spelling	oai:doaj.org-article:28ea0aa900874ae1b47854de5fbcc3c02021-12-02T17:51:06ZIncorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets10.1038/s41598-021-88446-72045-2322https://doaj.org/article/28ea0aa900874ae1b47854de5fbcc3c02021-05-01T00:00:00Zhttps://doi.org/10.1038/s41598-021-88446-7https://doaj.org/toc/2045-2322Abstract 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-Bu4N][DyIII(BH4)4] (1) and [Ph4P][DyIII(BH4)4] (2), involving DyIII centers surrounded by four pseudo-tetrahedrally arranged BH4 – ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I41/a), 1 crystallizes in a less symmetric monoclinic unit cell (P21/c). They exhibit yellow room-temperature photoluminescence related to the f–f electronic transitions. Moreover, they reveal DyIII-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-Bu4N][YIII 0.9DyIII 0.1(BH4)4] (1@Y) and [Ph4P][YIII 0.9DyIII 0.1(BH4)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 DyIII complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1–2 and the highly symmetrical inorganic DyIII borohydrides, α/β-Dy(BH4)3, 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of DyIII 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.Wojciech WegnerJakub J. ZakrzewskiMikolaj ZychowiczSzymon ChorazyNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 11, Iss 1, Pp 1-13 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Wojciech Wegner Jakub J. Zakrzewski Mikolaj Zychowicz Szymon Chorazy Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets
description	Abstract 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-Bu4N][DyIII(BH4)4] (1) and [Ph4P][DyIII(BH4)4] (2), involving DyIII centers surrounded by four pseudo-tetrahedrally arranged BH4 – ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I41/a), 1 crystallizes in a less symmetric monoclinic unit cell (P21/c). They exhibit yellow room-temperature photoluminescence related to the f–f electronic transitions. Moreover, they reveal DyIII-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-Bu4N][YIII 0.9DyIII 0.1(BH4)4] (1@Y) and [Ph4P][YIII 0.9DyIII 0.1(BH4)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 DyIII complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1–2 and the highly symmetrical inorganic DyIII borohydrides, α/β-Dy(BH4)3, 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of DyIII 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	article
author	Wojciech Wegner Jakub J. Zakrzewski Mikolaj Zychowicz Szymon Chorazy
author_facet	Wojciech Wegner Jakub J. Zakrzewski Mikolaj Zychowicz Szymon Chorazy
author_sort	Wojciech Wegner
title	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_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_sort	incorporation of expanded organic cations in dysprosium(iii) borohydrides for achieving luminescent molecular nanomagnets
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/28ea0aa900874ae1b47854de5fbcc3c0
work_keys_str_mv	AT wojciechwegner incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets AT jakubjzakrzewski incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets AT mikolajzychowicz incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets AT szymonchorazy incorporationofexpandedorganiccationsindysprosiumiiiborohydridesforachievingluminescentmolecularnanomagnets
_version_	1718379274572922880

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

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