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

Suryadevara, Nithin 1; Mizuno, Asato 1; Spieker, Lea; Salamon, Soma; Sleziona, Stephan; Maas, André; Pollmann, Erik; Heinrich, Benoît; Schleberger, Marika ; Wende, Heiko ; Kuppusamy, Senthil Kumar ORCID iD icon 2; Ruben, Mario 1,2
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)
2 Institut für QuantenMaterialien und Technologien (IQMT), Karlsruher Institut für Technologie (KIT)

Abstract:

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.


Verlagsausgabe §
DOI: 10.5445/IR/1000143655
Veröffentlicht am 10.03.2022
Originalveröffentlichung
DOI: 10.1002/chem.202103853
Scopus
Zitationen: 14
Web of Science
Zitationen: 15
Dimensions
Zitationen: 15
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Institut für QuantenMaterialien und Technologien (IQMT)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 27.01.2022
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000143655
HGF-Programm 47.12.02 (POF IV, LK 01) Exploratory Qubits
Erschienen in Chemistry – A European Journal
Verlag John Wiley and Sons
Band 28
Heft 6
Seiten Art.-Nr.: e202103853
Vorab online veröffentlicht am 19.01.2022
Nachgewiesen in Web of Science
Dimensions
Scopus
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