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Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals

[Image: see text] The ab initio calculations were correlated with magnetic and emission characteristics to understand the modulation of properties of NIR-emissive [Yb(III)(2,2′-bipyridine-1,1′-dioxide)(4)](3+) single-molecule magnets by cyanido/thiocyanidometallate counterions, [Ag(I)(CN)(2)](−) (1)...

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Autores principales: Zakrzewski, Jakub J., Kumar, Kunal, Zychowicz, Mikolaj, Jankowski, Robert, Wyczesany, Maciej, Sieklucka, Barbara, Ohkoshi, Shin-ichi, Chorazy, Szymon
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8573772/
https://www.ncbi.nlm.nih.gov/pubmed/34694818
http://dx.doi.org/10.1021/acs.jpclett.1c02942
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author Zakrzewski, Jakub J.
Kumar, Kunal
Zychowicz, Mikolaj
Jankowski, Robert
Wyczesany, Maciej
Sieklucka, Barbara
Ohkoshi, Shin-ichi
Chorazy, Szymon
author_facet Zakrzewski, Jakub J.
Kumar, Kunal
Zychowicz, Mikolaj
Jankowski, Robert
Wyczesany, Maciej
Sieklucka, Barbara
Ohkoshi, Shin-ichi
Chorazy, Szymon
author_sort Zakrzewski, Jakub J.
collection PubMed
description [Image: see text] The ab initio calculations were correlated with magnetic and emission characteristics to understand the modulation of properties of NIR-emissive [Yb(III)(2,2′-bipyridine-1,1′-dioxide)(4)](3+) single-molecule magnets by cyanido/thiocyanidometallate counterions, [Ag(I)(CN)(2)](−) (1), [Au(I)(SCN)(2)](−) (2), [Cd(II)(CN)(4)](2–)/[Cd(II)(2)(CN)(7)](3–) (3), and [M(III)(CN)(6)](3–) [M(III) = Co (4), Ir (5), Fe (6), Cr (7)]. Theoretical studies indicate easy-axis-type ground doublets for all Yb(III) centers. They differ in the magnetic axiality; however, transversal g-tensor components are always large enough to explain the lack of zero-dc-field relaxation. The excited doublets lie more than 120 cm(–1) above the ground one for all Yb(III) centers. It was confirmed by high-resolution emission spectra reproduced from the ab initio calculations that give reliable insight into energies and oscillator strengths of optical transitions. These findings indicate the dominance of Raman relaxation with the power n varying from 2.93(4) to 6.9(2) in the 4–3–5–1–2 series. This trend partially follows the magnetic axiality, being deeper correlated with the phonon modes schemes of (thio)cyanido matrices.
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spelling pubmed-85737722021-11-09 Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals Zakrzewski, Jakub J. Kumar, Kunal Zychowicz, Mikolaj Jankowski, Robert Wyczesany, Maciej Sieklucka, Barbara Ohkoshi, Shin-ichi Chorazy, Szymon J Phys Chem Lett [Image: see text] The ab initio calculations were correlated with magnetic and emission characteristics to understand the modulation of properties of NIR-emissive [Yb(III)(2,2′-bipyridine-1,1′-dioxide)(4)](3+) single-molecule magnets by cyanido/thiocyanidometallate counterions, [Ag(I)(CN)(2)](−) (1), [Au(I)(SCN)(2)](−) (2), [Cd(II)(CN)(4)](2–)/[Cd(II)(2)(CN)(7)](3–) (3), and [M(III)(CN)(6)](3–) [M(III) = Co (4), Ir (5), Fe (6), Cr (7)]. Theoretical studies indicate easy-axis-type ground doublets for all Yb(III) centers. They differ in the magnetic axiality; however, transversal g-tensor components are always large enough to explain the lack of zero-dc-field relaxation. The excited doublets lie more than 120 cm(–1) above the ground one for all Yb(III) centers. It was confirmed by high-resolution emission spectra reproduced from the ab initio calculations that give reliable insight into energies and oscillator strengths of optical transitions. These findings indicate the dominance of Raman relaxation with the power n varying from 2.93(4) to 6.9(2) in the 4–3–5–1–2 series. This trend partially follows the magnetic axiality, being deeper correlated with the phonon modes schemes of (thio)cyanido matrices. American Chemical Society 2021-10-25 2021-11-04 /pmc/articles/PMC8573772/ /pubmed/34694818 http://dx.doi.org/10.1021/acs.jpclett.1c02942 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 Zakrzewski, Jakub J.
Kumar, Kunal
Zychowicz, Mikolaj
Jankowski, Robert
Wyczesany, Maciej
Sieklucka, Barbara
Ohkoshi, Shin-ichi
Chorazy, Szymon
Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals
title Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals
title_full Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals
title_fullStr Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals
title_full_unstemmed Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals
title_short Combined Experimental and Ab Initio Methods for Rationalization of Magneto-Luminescent Properties of Yb(III) Nanomagnets Embedded in Cyanido/Thiocyanidometallate-Based Crystals
title_sort combined experimental and ab initio methods for rationalization of magneto-luminescent properties of yb(iii) nanomagnets embedded in cyanido/thiocyanidometallate-based crystals
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8573772/
https://www.ncbi.nlm.nih.gov/pubmed/34694818
http://dx.doi.org/10.1021/acs.jpclett.1c02942
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