Cargando…
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)...
Autores principales: | , , , , , , , , , , , |
---|---|
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 |
_version_ | 1784752264563392512 |
---|---|
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. |
format | Online Article Text |
id | pubmed-9305185 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT suryadevaranithin structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT mizunoasato structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT spiekerlea structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT salamonsoma structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT slezionastephan structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT maasandre structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT pollmannerik structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT heinrichbenoit structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT schlebergermarika structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT wendeheiko structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT kuppusamysenthilkumar structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes AT rubenmario structuralinsightsintohystereticspincrossoverinasetofironii26bis1hpyrazol1ylpyridinecomplexes |