Peculiar Spin-Crossover Behavior in the 2D Polymer K[FeIII(5Cl-thsa)2]
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 natur...
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creator | Spitsyna, Nataliya G Blagov, Maxim A Lazarenko, Vladimir A Svetogorov, Roman D Zubavichus, Yan V Zorina, Leokadiya V Maximova, Olga Yaroslavtsev, Sergey A Rusakov, Vyacheslav S Raganyan, Grigory V Yagubskii, Eduard B Vasiliev, Alexander N |
description | 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 T 1/2 = 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. |
doi_str_mv | 10.1021/acs.inorgchem.1c01821 |
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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 T 1/2 = 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.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/acs.inorgchem.1c01821</identifier><identifier>PMID: 34757728</identifier><language>eng</language><publisher>WASHINGTON: American Chemical Society</publisher><subject>Chemistry ; Chemistry, Inorganic & Nuclear ; Physical Sciences ; Science & Technology</subject><ispartof>Inorganic chemistry, 2021-12, Vol.60 (23), p.17462-17479</ispartof><rights>2021 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>true</woscitedreferencessubscribed><woscitedreferencescount>6</woscitedreferencescount><woscitedreferencesoriginalsourcerecordid>wos000753441100008</woscitedreferencesoriginalsourcerecordid><citedby>FETCH-LOGICAL-a328t-abb9f0343e1d11411a5a97e980be24f9eb6c34be807b508f43563dc21812992f3</citedby><cites>FETCH-LOGICAL-a328t-abb9f0343e1d11411a5a97e980be24f9eb6c34be807b508f43563dc21812992f3</cites><orcidid>0000-0002-0115-4103 ; 0000-0001-8342-5474 ; 0000-0001-7789-6683 ; 0000-0002-7159-5123 ; 0000-0002-3012-8967 ; 0000-0003-2266-8944 ; 0000-0003-3558-6761 ; 0000-0001-7185-3041 ; 0000-0003-1024-6461 ; 0000-0003-0360-1023 ; 0000-0001-0360-1023 ; 0000-0002-3613-9763</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.1c01821$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.1c01821$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>315,782,786,2767,27083,27931,27932,39265,56745,56795</link.rule.ids></links><search><creatorcontrib>Spitsyna, Nataliya G</creatorcontrib><creatorcontrib>Blagov, Maxim A</creatorcontrib><creatorcontrib>Lazarenko, Vladimir A</creatorcontrib><creatorcontrib>Svetogorov, Roman D</creatorcontrib><creatorcontrib>Zubavichus, Yan V</creatorcontrib><creatorcontrib>Zorina, Leokadiya V</creatorcontrib><creatorcontrib>Maximova, Olga</creatorcontrib><creatorcontrib>Yaroslavtsev, Sergey A</creatorcontrib><creatorcontrib>Rusakov, Vyacheslav S</creatorcontrib><creatorcontrib>Raganyan, Grigory V</creatorcontrib><creatorcontrib>Yagubskii, Eduard B</creatorcontrib><creatorcontrib>Vasiliev, Alexander N</creatorcontrib><title>Peculiar Spin-Crossover Behavior in the 2D Polymer K[FeIII(5Cl-thsa)2]</title><title>Inorganic chemistry</title><addtitle>INORG CHEM</addtitle><addtitle>Inorg. Chem</addtitle><description>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 T 1/2 = 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. 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Chem</addtitle><date>2021-12-06</date><risdate>2021</risdate><volume>60</volume><issue>23</issue><spage>17462</spage><epage>17479</epage><pages>17462-17479</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><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 T 1/2 = 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.</abstract><cop>WASHINGTON</cop><pub>American Chemical Society</pub><pmid>34757728</pmid><doi>10.1021/acs.inorgchem.1c01821</doi><tpages>18</tpages><orcidid>https://orcid.org/0000-0002-0115-4103</orcidid><orcidid>https://orcid.org/0000-0001-8342-5474</orcidid><orcidid>https://orcid.org/0000-0001-7789-6683</orcidid><orcidid>https://orcid.org/0000-0002-7159-5123</orcidid><orcidid>https://orcid.org/0000-0002-3012-8967</orcidid><orcidid>https://orcid.org/0000-0003-2266-8944</orcidid><orcidid>https://orcid.org/0000-0003-3558-6761</orcidid><orcidid>https://orcid.org/0000-0001-7185-3041</orcidid><orcidid>https://orcid.org/0000-0003-1024-6461</orcidid><orcidid>https://orcid.org/0000-0003-0360-1023</orcidid><orcidid>https://orcid.org/0000-0001-0360-1023</orcidid><orcidid>https://orcid.org/0000-0002-3613-9763</orcidid></addata></record> |
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title | Peculiar Spin-Crossover Behavior in the 2D Polymer K[FeIII(5Cl-thsa)2] |
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