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Cooperative Spin Crossover above Room Temperature in the Iron(II) Cyanoborohydride–Pyrazine Complex
Department of Chemistry, Taras Shevchenko National University of Kyiv, 64 Volodymyrska St., 01601 Kyiv, Ukraine.
“Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, 700487 Iaşi, Romania.
Faculty of Electrical Engineering and Computer Science & MANSiD Research Center, Ştefan cel Mare University, Universitatii St. 13, 720229 Suceava, Romania.ORCID iD: 0000-0002-8782-7988
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.ORCID iD: 0000-0003-2104-1912
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2022 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 61, no 37, p. 14761-14769Article in journal (Refereed) Published
Abstract [en]

Hysteretic spin crossover in coordination complexes of 3d-metal ions represents one of the most spectacular phenomena of molecular bistability. In this paper we describe a self-assembly of pyrazine (pz) and Fe(BH3CN)2 that afforded the new 2D coordination polymer [Fe(pz)2(BH3CN)2]. It undergoes an abrupt, hysteretic spin crossover (SCO) with a T1/2 of 338 K (heating) and 326 K (cooling) according to magnetic susceptibility measurements. Mössbauer spectroscopy revealed a complete transition between the low-spin (LS) and the high-spin (HS) states of the iron centers. This LS-to-HS transition induced an increase of the unit cell volume by 10.6%. Meanwhile, a modulation of multiple [C–Hδ+···Hδ−–B] dihydrogen bonds stimulates a contraction in direction c (2.2%). The simplicity of the synthesis, mild temperatures of transition, a pronounced thermochromism, stability upon thermal cycling, a striking volume expansion upon SCO, and an easy processability to composite films make this new complex an attractive material for switchable components of diverse applications.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2022. Vol. 61, no 37, p. 14761-14769
Keywords [en]
Spin transition, spin crossover, iron complexes, magnetism, spin state
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-486019DOI: 10.1021/acs.inorgchem.2c02177ISI: 000855253700001PubMedID: 36067517OAI: oai:DiVA.org:uu-486019DiVA, id: diva2:1700295
Available from: 2022-09-30 Created: 2022-09-30 Last updated: 2022-09-30Bibliographically approved

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Shylin, Sergii I.

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