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Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes

Bistable spin‐crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT (1/2)) spin‐state switching are desirable for molecule‐based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)‐2,6‐bis(1H‐pyrazol‐1‐yl)pyridine)...

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Detalles Bibliográficos
Autores principales: Suryadevara, Nithin, Mizuno, Asato, Spieker, Lea, Salamon, Soma, Sleziona, Stephan, Maas, André, Pollmann, Erik, Heinrich, Benoît, Schleberger, Marika, Wende, Heiko, Kuppusamy, Senthil Kumar, Ruben, Mario
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9305185/
https://www.ncbi.nlm.nih.gov/pubmed/34939670
http://dx.doi.org/10.1002/chem.202103853
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author Suryadevara, Nithin
Mizuno, Asato
Spieker, Lea
Salamon, Soma
Sleziona, Stephan
Maas, André
Pollmann, Erik
Heinrich, Benoît
Schleberger, Marika
Wende, Heiko
Kuppusamy, Senthil Kumar
Ruben, Mario
author_facet Suryadevara, Nithin
Mizuno, Asato
Spieker, Lea
Salamon, Soma
Sleziona, Stephan
Maas, André
Pollmann, Erik
Heinrich, Benoît
Schleberger, Marika
Wende, Heiko
Kuppusamy, Senthil Kumar
Ruben, Mario
author_sort Suryadevara, Nithin
collection PubMed
description Bistable spin‐crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT (1/2)) spin‐state switching are desirable for molecule‐based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)‐2,6‐bis(1H‐pyrazol‐1‐yl)pyridine) (bpp) complexes – [Fe(bpp−COOEt)(2)](X)(2) ⋅CH(3)NO(2) (X=ClO(4), 1; X=BF(4), 2). Stable spin‐state switching – T (1/2)=288 K; ΔT (1/2)=62 K – is observed for 1, whereas 2 undergoes above‐room‐temperature lattice‐solvent content‐dependent SCO – T (1/2)=331 K; ΔT (1/2)=43 K. Variable‐temperature single‐crystal X‐ray diffraction studies of the complexes revealed pronounced molecular reorganizations – from the Jahn‐Teller‐distorted HS state to the less distorted LS state – and conformation switching of the ethyl group of the COOEt substituent upon SCO. Consequently, we propose that the large structural reorganizations rendered SCO hysteretic in 1 and 2. Such insights shedding light on the molecular origin of thermal hysteresis might enable the design of technologically relevant molecule‐based switching and memory elements.
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spelling pubmed-93051852022-07-28 Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes Suryadevara, Nithin Mizuno, Asato Spieker, Lea Salamon, Soma Sleziona, Stephan Maas, André Pollmann, Erik Heinrich, Benoît Schleberger, Marika Wende, Heiko Kuppusamy, Senthil Kumar Ruben, Mario Chemistry Research Articles Bistable spin‐crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT (1/2)) spin‐state switching are desirable for molecule‐based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)‐2,6‐bis(1H‐pyrazol‐1‐yl)pyridine) (bpp) complexes – [Fe(bpp−COOEt)(2)](X)(2) ⋅CH(3)NO(2) (X=ClO(4), 1; X=BF(4), 2). Stable spin‐state switching – T (1/2)=288 K; ΔT (1/2)=62 K – is observed for 1, whereas 2 undergoes above‐room‐temperature lattice‐solvent content‐dependent SCO – T (1/2)=331 K; ΔT (1/2)=43 K. Variable‐temperature single‐crystal X‐ray diffraction studies of the complexes revealed pronounced molecular reorganizations – from the Jahn‐Teller‐distorted HS state to the less distorted LS state – and conformation switching of the ethyl group of the COOEt substituent upon SCO. Consequently, we propose that the large structural reorganizations rendered SCO hysteretic in 1 and 2. Such insights shedding light on the molecular origin of thermal hysteresis might enable the design of technologically relevant molecule‐based switching and memory elements. John Wiley and Sons Inc. 2022-01-19 2022-01-27 /pmc/articles/PMC9305185/ /pubmed/34939670 http://dx.doi.org/10.1002/chem.202103853 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ (https://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
spellingShingle Research Articles
Suryadevara, Nithin
Mizuno, Asato
Spieker, Lea
Salamon, Soma
Sleziona, Stephan
Maas, André
Pollmann, Erik
Heinrich, Benoît
Schleberger, Marika
Wende, Heiko
Kuppusamy, Senthil Kumar
Ruben, Mario
Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes
title Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes
title_full Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes
title_fullStr Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes
title_full_unstemmed Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes
title_short Structural Insights into Hysteretic Spin‐Crossover in a Set of Iron(II)‐2,6‐bis(1H‐Pyrazol‐1‐yl)Pyridine) Complexes
title_sort structural insights into hysteretic spin‐crossover in a set of iron(ii)‐2,6‐bis(1h‐pyrazol‐1‐yl)pyridine) complexes
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9305185/
https://www.ncbi.nlm.nih.gov/pubmed/34939670
http://dx.doi.org/10.1002/chem.202103853
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