Peculiar Spin-Crossover Behavior in the 2D Polymer K[FeIII(5Cl-thsa)2] Full article
| Journal |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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| Output data | Year: 2021, Volume: 60, Number: 23, Pages: 17462-17479 Pages count : 18 DOI: 10.1021/acs.inorgchem.1c01821 | ||||||||||||
| Tags | Chlorine compounds; Electrospinning; Hysteresis; Iron compounds; Magnetic materials; Magnetic moments; Phenols | ||||||||||||
| Authors |
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| Affiliations |
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Funding (4)
| 1 | Ministry of Science and Higher Education of the Russian Federation | 0089-2019-0011 (АААА-А19-119092390079-8) |
| 2 | Ministry of Science and Higher Education of the Russian Federation | ГЗ-2021-2023 |
| 3 | Ministry of Science and Higher Education of the Russian Federation | 075-15-2021-604 |
| 4 | Ministry of Science and Higher Education of the Russian Federation |
Abstract:
A potassium salt of the N2S2O2-coordination Fe(III) anion K[Fe(5Cl-thsa)2] (1)
(5Cl-thsa − 5-chlorosalicylaldehyde thiosemicarbazone) is synthesized and characterized structurally and magnetically over a wide temperature range. Two polymorphs of salt 1 characterized by the common 2D polymer nature and assigned to the same orthorhombic Pbcn space group have been identified. The molecular structure of the minor polymorph of 1 was solved and refined at 100, 250, and 300 K is shown to correspond to the LS configuration. The dominant polymorph of 1 features K+ cations disordered over a few crystallographic sites, while the minor polymorph includes fully ordered K+ cations. The major polymorph exhibits a complete three-step cooperative spin-crossover transition both in the heating and cooling modes: The first step occurs in a temperature range from 2 to 50 K; the second abrupt hysteretic step occurs from 200 to 250 K with T1/2 = 230 K and a 6 K hysteresis loop. The third gradual step occurs from 250 to 440 K. According to 57Fe Mössbauer, XRPD, and EXAFS data, the spin-crossover transition for the dominant polymorph is quite peculiar. Indeed, the increase in the HS concentration by 57% at the second step does not result in the expected significant increase in the iron(III)–ligand bond lengths. In addition, the final step of the spin conversion (ΔγHS = 26%) is associated with a structural phase transition with a symmetry lowering from the orthorhombic (Pbcn) to the monoclinic (P21/n) space group. This nontrivial phenomenon was investigated in detail by applying magnetization measurements, electron spin resonance, 57Fe Mössbauer spectroscopy, and DFT calculations. These results provide a new platform for understanding the multistep spin-crossover character in the Fe(III) thsa-complexes and related compounds.
Cite:
Spitsyna N.G.
, Blagov M.A.
, Lazarenko V.A.
, Svetogorov R.D.
, Zubavichus Y.V.
, Zorina L.V.
, Maximova O.
, Yaroslavtsev S.A.
, Rusakov V.S.
, Raganyan G.V.
, Yagubskii E.B.
, Vasiliev A.N.
Peculiar Spin-Crossover Behavior in the 2D Polymer K[FeIII(5Cl-thsa)2]
Inorganic Chemistry. 2021. V.60. N23. P.17462-17479. DOI: 10.1021/acs.inorgchem.1c01821 WOS Scopus РИНЦ ANCAN PMID OpenAlex publication_identifier_short.sciact_skif_identifier_type
Peculiar Spin-Crossover Behavior in the 2D Polymer K[FeIII(5Cl-thsa)2]
Inorganic Chemistry. 2021. V.60. N23. P.17462-17479. DOI: 10.1021/acs.inorgchem.1c01821 WOS Scopus РИНЦ ANCAN PMID OpenAlex publication_identifier_short.sciact_skif_identifier_type
Dates:
| Submitted: | Jun 16, 2021 |
| Published online: | Nov 10, 2021 |
| Published print: | Dec 6, 2021 |
Identifiers:
| Web of science: | WOS:000753441100008 |
| Scopus: | 2-s2.0-85119382657 |
| Elibrary: | 47526651 |
| Chemical Abstracts: | 2021:2451295 |
| Chemical Abstracts (print): | 177:14656 |
| PMID: | 34757728 |
| OpenAlex: | W3212713945 |
| publication_identifier.sciact_skif_identifier_type: | 500 |