Abrupt Spin Transition and Chiral Hydrogen-Bonded One-Dimensional Structure of Iron(III) Complex [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine)
Solvent-free spin crossover (SCO) iron(III) complex, [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine), is synthesized. The FeIII ion has an octahedral coordination geometry, with N2O2 donor atoms of hapen and N2 atoms of two imidazoles at the a...
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description | Solvent-free spin crossover (SCO) iron(III) complex, [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine), is synthesized. The FeIII ion has an octahedral coordination geometry, with N2O2 donor atoms of hapen and N2 atoms of two imidazoles at the axial positions. The saturated five-membered chelate ring of hapen moiety assumes a gauche-type δ- or λ-conformation to give chiral species of δ-[FeIII(Him)2(hapen)]+ or λ-[FeIII(Him)2(hapen)]+. One imidazole is hydrogen-bonded to phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded chiral one-dimensional structure, {δ-[FeIII(Him)2(hapen)]+}1∞ or {λ-[FeIII(Him)2(hapen)]+}1∞. The adjacent chains with the opposite chiralities are arrayed alternately. The temperature dependences of the magnetic susceptibilities revealed an abrupt one-step spin transition between high-spin (S = 5/2) and low-spin (S = 1/2) states at the spin transition temperature of T1/2 = 105 K. The crystal structures were determined at 296 and 100 K, where the populations of HS:LS of high- and low-spin ratio are evaluated to be 1:0 and 0.3:0.7, respectively, based on magnetic measurements. During the spin transition from 296 K to 100 K, the average Fe–N distance and O–Fe–O angle decrease to a regular octahedron by 0.16 Å and 13.4°, respectively. The structural change in the coordination environment is transmitted to the adjacent spin crossover (SCO) sites along the chiral 1D chain through hydrogen-bonds. The abrupt SCO profile and the spin transition temperature for the isomorphous compounds [FeIII(Him)2(hapen)]Y (Y = PF6, AsF6, SbF6) are ascribed to the chiral hydrogen-bonded 1D structure and chain-anion interaction. |
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The FeIII ion has an octahedral coordination geometry, with N2O2 donor atoms of hapen and N2 atoms of two imidazoles at the axial positions. The saturated five-membered chelate ring of hapen moiety assumes a gauche-type δ- or λ-conformation to give chiral species of δ-[FeIII(Him)2(hapen)]+ or λ-[FeIII(Him)2(hapen)]+. One imidazole is hydrogen-bonded to phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded chiral one-dimensional structure, {δ-[FeIII(Him)2(hapen)]+}1∞ or {λ-[FeIII(Him)2(hapen)]+}1∞. The adjacent chains with the opposite chiralities are arrayed alternately. The temperature dependences of the magnetic susceptibilities revealed an abrupt one-step spin transition between high-spin (S = 5/2) and low-spin (S = 1/2) states at the spin transition temperature of T1/2 = 105 K. The crystal structures were determined at 296 and 100 K, where the populations of HS:LS of high- and low-spin ratio are evaluated to be 1:0 and 0.3:0.7, respectively, based on magnetic measurements. During the spin transition from 296 K to 100 K, the average Fe–N distance and O–Fe–O angle decrease to a regular octahedron by 0.16 Å and 13.4°, respectively. The structural change in the coordination environment is transmitted to the adjacent spin crossover (SCO) sites along the chiral 1D chain through hydrogen-bonds. The abrupt SCO profile and the spin transition temperature for the isomorphous compounds [FeIII(Him)2(hapen)]Y (Y = PF6, AsF6, SbF6) are ascribed to the chiral hydrogen-bonded 1D structure and chain-anion interaction.</description><identifier>ISSN: 2312-7481</identifier><identifier>EISSN: 2312-7481</identifier><identifier>DOI: 10.3390/magnetochemistry1010072</identifier><language>eng</language><publisher>Basel: MDPI AG</publisher><subject>Chains ; Chelates ; Chemical synthesis ; Crossovers ; Crystal structure ; Equilibrium ; Ethylenediamine ; Hydrogen bonding ; Hydrogen bonds ; Imidazole ; Iron ; Ligands ; Magnetic measurement ; Nitrogen ; Phase transitions ; Spin transition ; Transition temperature</subject><ispartof>Magnetochemistry, 2015-12, Vol.1 (1), p.72-82</ispartof><rights>2015. This work is licensed under http://creativecommons.org/licenses/by/3.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1792-6e267b6a777a0a59e8bb62aca0424280d1495bb6067379b0cae5759b3d6daff63</citedby><cites>FETCH-LOGICAL-c1792-6e267b6a777a0a59e8bb62aca0424280d1495bb6067379b0cae5759b3d6daff63</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,864,27923,27924</link.rule.ids></links><search><creatorcontrib>Ueno, Takahiro</creatorcontrib><creatorcontrib>Miyano, Kyohei</creatorcontrib><creatorcontrib>Hamada, Daisuke</creatorcontrib><creatorcontrib>Ono, Hiromasa</creatorcontrib><creatorcontrib>Fujinami, Takeshi</creatorcontrib><creatorcontrib>Matsumoto, Naohide</creatorcontrib><creatorcontrib>Sunatsuki, Yukinari</creatorcontrib><title>Abrupt Spin Transition and Chiral Hydrogen-Bonded One-Dimensional Structure of Iron(III) Complex [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine)</title><title>Magnetochemistry</title><description>Solvent-free spin crossover (SCO) iron(III) complex, [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine), is synthesized. The FeIII ion has an octahedral coordination geometry, with N2O2 donor atoms of hapen and N2 atoms of two imidazoles at the axial positions. The saturated five-membered chelate ring of hapen moiety assumes a gauche-type δ- or λ-conformation to give chiral species of δ-[FeIII(Him)2(hapen)]+ or λ-[FeIII(Him)2(hapen)]+. One imidazole is hydrogen-bonded to phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded chiral one-dimensional structure, {δ-[FeIII(Him)2(hapen)]+}1∞ or {λ-[FeIII(Him)2(hapen)]+}1∞. The adjacent chains with the opposite chiralities are arrayed alternately. The temperature dependences of the magnetic susceptibilities revealed an abrupt one-step spin transition between high-spin (S = 5/2) and low-spin (S = 1/2) states at the spin transition temperature of T1/2 = 105 K. The crystal structures were determined at 296 and 100 K, where the populations of HS:LS of high- and low-spin ratio are evaluated to be 1:0 and 0.3:0.7, respectively, based on magnetic measurements. During the spin transition from 296 K to 100 K, the average Fe–N distance and O–Fe–O angle decrease to a regular octahedron by 0.16 Å and 13.4°, respectively. The structural change in the coordination environment is transmitted to the adjacent spin crossover (SCO) sites along the chiral 1D chain through hydrogen-bonds. The abrupt SCO profile and the spin transition temperature for the isomorphous compounds [FeIII(Him)2(hapen)]Y (Y = PF6, AsF6, SbF6) are ascribed to the chiral hydrogen-bonded 1D structure and chain-anion interaction.</description><subject>Chains</subject><subject>Chelates</subject><subject>Chemical synthesis</subject><subject>Crossovers</subject><subject>Crystal structure</subject><subject>Equilibrium</subject><subject>Ethylenediamine</subject><subject>Hydrogen bonding</subject><subject>Hydrogen bonds</subject><subject>Imidazole</subject><subject>Iron</subject><subject>Ligands</subject><subject>Magnetic measurement</subject><subject>Nitrogen</subject><subject>Phase transitions</subject><subject>Spin transition</subject><subject>Transition temperature</subject><issn>2312-7481</issn><issn>2312-7481</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><sourceid>ABUWG</sourceid><sourceid>AFKRA</sourceid><sourceid>AZQEC</sourceid><sourceid>BENPR</sourceid><sourceid>CCPQU</sourceid><sourceid>DWQXO</sourceid><recordid>eNp1UU1u1DAUjhBIVG3PgCU2M1JT_JPYkwWLMjBMpKpdTFkhFL3EL42rxA52IjWsOBPX4BacBA9lwYbV-_709H6S5BWjl0IU9M0A9xYn13Q4mDD5hVFGqeLPkhMuGE9VtmHP_8Evk_MQHiilnDKheHGS_Lyq_TxO5DAaS-482GAm4ywBq8m2Mx56sl-0d_do03fOatTk1mL63gwYo85G_zD5uZlmj8S1pPTOrsqyXJOtG8YeH8nnHUa-2pthzVcdjGjXXw71TpKjRN4SMxgN31yPF2TP__hRvLm4-fX9R1qbsOJpdxzgcYEmbjp2aJfeaLS4xqlb-gi0gcFEfpa8aKEPeP63niafdh_utvv0-vZjub26ThumCp5K5FLVEpRSQCEvcFPXkkMDNOMZ31DNsiKPEpVKqKKmDWCu8qIWWmpoWylOk9dPfUfvvs4YpurBzT6eIlSc8UzmijERU-op1XgXgse2Gr0ZwC8Vo9XxedV_nid-AyXRlEI</recordid><startdate>20151211</startdate><enddate>20151211</enddate><creator>Ueno, Takahiro</creator><creator>Miyano, Kyohei</creator><creator>Hamada, Daisuke</creator><creator>Ono, Hiromasa</creator><creator>Fujinami, Takeshi</creator><creator>Matsumoto, Naohide</creator><creator>Sunatsuki, Yukinari</creator><general>MDPI AG</general><scope>AAYXX</scope><scope>CITATION</scope><scope>8FE</scope><scope>8FG</scope><scope>ABJCF</scope><scope>ABUWG</scope><scope>AFKRA</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>HCIFZ</scope><scope>KB.</scope><scope>PDBOC</scope><scope>PIMPY</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>PRINS</scope></search><sort><creationdate>20151211</creationdate><title>Abrupt Spin Transition and Chiral Hydrogen-Bonded One-Dimensional Structure of Iron(III) Complex [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine)</title><author>Ueno, Takahiro ; Miyano, Kyohei ; Hamada, Daisuke ; Ono, Hiromasa ; Fujinami, Takeshi ; Matsumoto, Naohide ; Sunatsuki, Yukinari</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1792-6e267b6a777a0a59e8bb62aca0424280d1495bb6067379b0cae5759b3d6daff63</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Chains</topic><topic>Chelates</topic><topic>Chemical synthesis</topic><topic>Crossovers</topic><topic>Crystal structure</topic><topic>Equilibrium</topic><topic>Ethylenediamine</topic><topic>Hydrogen bonding</topic><topic>Hydrogen bonds</topic><topic>Imidazole</topic><topic>Iron</topic><topic>Ligands</topic><topic>Magnetic measurement</topic><topic>Nitrogen</topic><topic>Phase transitions</topic><topic>Spin transition</topic><topic>Transition temperature</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ueno, Takahiro</creatorcontrib><creatorcontrib>Miyano, Kyohei</creatorcontrib><creatorcontrib>Hamada, Daisuke</creatorcontrib><creatorcontrib>Ono, Hiromasa</creatorcontrib><creatorcontrib>Fujinami, Takeshi</creatorcontrib><creatorcontrib>Matsumoto, Naohide</creatorcontrib><creatorcontrib>Sunatsuki, Yukinari</creatorcontrib><collection>CrossRef</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>Materials Science & Engineering Collection</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central Essentials</collection><collection>ProQuest Central</collection><collection>Technology Collection (ProQuest)</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central Korea</collection><collection>SciTech Premium Collection</collection><collection>Materials Science Database</collection><collection>Materials Science Collection</collection><collection>Publicly Available Content Database</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>ProQuest Central China</collection><jtitle>Magnetochemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ueno, Takahiro</au><au>Miyano, Kyohei</au><au>Hamada, Daisuke</au><au>Ono, Hiromasa</au><au>Fujinami, Takeshi</au><au>Matsumoto, Naohide</au><au>Sunatsuki, Yukinari</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Abrupt Spin Transition and Chiral Hydrogen-Bonded One-Dimensional Structure of Iron(III) Complex [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine)</atitle><jtitle>Magnetochemistry</jtitle><date>2015-12-11</date><risdate>2015</risdate><volume>1</volume><issue>1</issue><spage>72</spage><epage>82</epage><pages>72-82</pages><issn>2312-7481</issn><eissn>2312-7481</eissn><abstract>Solvent-free spin crossover (SCO) iron(III) complex, [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine), is synthesized. The FeIII ion has an octahedral coordination geometry, with N2O2 donor atoms of hapen and N2 atoms of two imidazoles at the axial positions. The saturated five-membered chelate ring of hapen moiety assumes a gauche-type δ- or λ-conformation to give chiral species of δ-[FeIII(Him)2(hapen)]+ or λ-[FeIII(Him)2(hapen)]+. One imidazole is hydrogen-bonded to phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded chiral one-dimensional structure, {δ-[FeIII(Him)2(hapen)]+}1∞ or {λ-[FeIII(Him)2(hapen)]+}1∞. The adjacent chains with the opposite chiralities are arrayed alternately. The temperature dependences of the magnetic susceptibilities revealed an abrupt one-step spin transition between high-spin (S = 5/2) and low-spin (S = 1/2) states at the spin transition temperature of T1/2 = 105 K. The crystal structures were determined at 296 and 100 K, where the populations of HS:LS of high- and low-spin ratio are evaluated to be 1:0 and 0.3:0.7, respectively, based on magnetic measurements. During the spin transition from 296 K to 100 K, the average Fe–N distance and O–Fe–O angle decrease to a regular octahedron by 0.16 Å and 13.4°, respectively. The structural change in the coordination environment is transmitted to the adjacent spin crossover (SCO) sites along the chiral 1D chain through hydrogen-bonds. The abrupt SCO profile and the spin transition temperature for the isomorphous compounds [FeIII(Him)2(hapen)]Y (Y = PF6, AsF6, SbF6) are ascribed to the chiral hydrogen-bonded 1D structure and chain-anion interaction.</abstract><cop>Basel</cop><pub>MDPI AG</pub><doi>10.3390/magnetochemistry1010072</doi><tpages>11</tpages><oa>free_for_read</oa></addata></record> |
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subjects | Chains Chelates Chemical synthesis Crossovers Crystal structure Equilibrium Ethylenediamine Hydrogen bonding Hydrogen bonds Imidazole Iron Ligands Magnetic measurement Nitrogen Phase transitions Spin transition Transition temperature |
title | Abrupt Spin Transition and Chiral Hydrogen-Bonded One-Dimensional Structure of Iron(III) Complex [FeIII(Him)2(hapen)]SbF6 (Him = imidazole, H2hapen = N,N′-bis(2-hydroxyacetophenylidene)ethylenediamine) |
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