Pronounced Magnetic Bistability in Highly Cooperative Mononuclear [Fe(L npdtz ) 2 (NCX) 2 ] Complexes

Molecular materials that exhibit stimuli-responsive bistability are promising candidates for the development of molecular switches and sensors. We herein report on the coexistence of a wide thermal hysteretic spin crossover (SCO) effect and a thermally inducible metastable high-spin state at low tem...

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Bibliographic Details
Published in:Inorganic chemistry Vol. 61; no. 7; p. 3141
Main Authors: Kiehl, Jonathan, Hochdörffer, Tim, Carrella, Luca M, Schünemann, Volker, Nygaard, Mathilde H, Overgaard, Jacob, Rentschler, Eva
Format: Journal Article
Language:English
Published: United States 21.02.2022
ISSN:1520-510X
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Summary:Molecular materials that exhibit stimuli-responsive bistability are promising candidates for the development of molecular switches and sensors. We herein report on the coexistence of a wide thermal hysteretic spin crossover (SCO) effect and a thermally inducible metastable high-spin state at low temperatures achieved with the two new complexes [Fe (L ) (NCX) ] (X = S; Se), with L being (2-naphthyl-5-pyridyl-1,2,4-thiadiazole) and X = S ( ) and Se ( ). Pronounced π-π-stacking of the aromatic side residues of the ligands enables strong intermolecular interactions, leading to abrupt SCO properties and broad magnetic hysteresis of 10 K for X = S and 58 K for X = Se. In this paper, we also present the pressure-induced spin-state switching around 0.8 GPa. A pronounced thermally induced excited spin state trapping (TIESST effect) is observed for the highly cooperative SCO compounds, which was experimentally followed by low-temperature single crystal structure analysis (20 K) and temperature-dependent Mössbauer spectroscopy.
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.1c03491