Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations
Inspired by the reported crystal structure of compound 1, we aimed to synthesize and determine the structure of compound 2, where two imidazolium (H2im+) ions serve as diamagnetic countercations. Here, we report the thermal stabilities, FT–IR, visible, and RSE spectra, as well as the magnetic proper...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/375464 |
| Acceso en línea: | http://hdl.handle.net/10261/375464 |
| Access Level: | acceso abierto |
| Palabra clave: | Copper(II) Linear trinuclear complex Crystal structure Thermogravimetry Spectral properties Magnetism DFT calculations |
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Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT CalculationsBelmont-Sánchez, Jeannette CarolinaChoquesillo-Lazarte, DuaneFrontera, AntonioLezama, LuisCastiñeiras, AlfonsoNiclós-Gutiérrez, JuanCopper(II)Linear trinuclear complexCrystal structureThermogravimetrySpectral propertiesMagnetismDFT calculationsInspired by the reported crystal structure of compound 1, we aimed to synthesize and determine the structure of compound 2, where two imidazolium (H2im+) ions serve as diamagnetic countercations. Here, we report the thermal stabilities, FT–IR, visible, and RSE spectra, as well as the magnetic properties of both compounds. In these structures, µ-EDTA acts as a pentadentate chelator for both terminal Cu centers within the centrosymmetric linear trinuclear anion. The Cu(µ-EDTA) chelates bind to the central Cu(Him)4 unit in subtly different ways: in compound 1, µ-EDTA has a free acetate arm and binds the central Cu(II) center through a syn,anti-carboxylate group. In contrast, in compound 2, the non-chelating acetate arm serves as a monodentate O-donor to the central Cu(II) atom, increasing the Cu(terminal)···Cu(central) distance from 6.08 Å in 1 to 6.80 Å in 2. Additionally, pairs of H2im+ ions in compound 2 display antiparallel π-stacking interactions. We conclude that the H2im+ counterions in compound 2 enable the magnetic isolation of the nearly identical trinuclear anion present in both compounds. DFT calculations further support the role of different interactions in stabilizing each crystal structure. In compound 2, dominant contributions from N–H···O hydrogen bonds and π-stacking interactions are accompanied by other, less conventional interactions, such as multiple C–H···O contacts and an O···CO(π-hole) interaction within the trinuclear anion.We thank the financial support from the Spain Ministry of Science, Innovation and Universities (MICIU/AEI of Spain; projects PID2020-115637GB-I00 and PID2023-148453NB-I00, FEDER funds). MICINN of Spain project PID2023-151538NB-I00 FEDER, Project B-FQM-478-UGR20 (FEDER-Universidad de Granada, Spain) and Research Group FQM-283 (Junta de Andalucía, Spain) are also acknowledged.Peer reviewedMultidisciplinary Digital Publishing InstituteMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)European CommissionUniversidad de GranadaJunta de AndalucíaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2025202520242025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/375464reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-115637GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-148453NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-151538NB-I00The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI https://doi.org/10.3390/ijms252313130https://doi.org/10.3390/ijms252313130Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3754642026-05-22T06:33:51Z |
| dc.title.none.fl_str_mv |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations |
| title |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations |
| spellingShingle |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations Belmont-Sánchez, Jeannette Carolina Copper(II) Linear trinuclear complex Crystal structure Thermogravimetry Spectral properties Magnetism DFT calculations |
| title_short |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations |
| title_full |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations |
| title_fullStr |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations |
| title_full_unstemmed |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations |
| title_sort |
Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(µ-EDTA)Cu(Him)}2]·2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations |
| dc.creator.none.fl_str_mv |
Belmont-Sánchez, Jeannette Carolina Choquesillo-Lazarte, Duane Frontera, Antonio Lezama, Luis Castiñeiras, Alfonso Niclós-Gutiérrez, Juan |
| author |
Belmont-Sánchez, Jeannette Carolina |
| author_facet |
Belmont-Sánchez, Jeannette Carolina Choquesillo-Lazarte, Duane Frontera, Antonio Lezama, Luis Castiñeiras, Alfonso Niclós-Gutiérrez, Juan |
| author_role |
author |
| author2 |
Choquesillo-Lazarte, Duane Frontera, Antonio Lezama, Luis Castiñeiras, Alfonso Niclós-Gutiérrez, Juan |
| author2_role |
author author author author author |
| dc.contributor.none.fl_str_mv |
Ministerio de Ciencia, Innovación y Universidades (España) Agencia Estatal de Investigación (España) European Commission Universidad de Granada Junta de Andalucía Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
Copper(II) Linear trinuclear complex Crystal structure Thermogravimetry Spectral properties Magnetism DFT calculations |
| topic |
Copper(II) Linear trinuclear complex Crystal structure Thermogravimetry Spectral properties Magnetism DFT calculations |
| description |
Inspired by the reported crystal structure of compound 1, we aimed to synthesize and determine the structure of compound 2, where two imidazolium (H2im+) ions serve as diamagnetic countercations. Here, we report the thermal stabilities, FT–IR, visible, and RSE spectra, as well as the magnetic properties of both compounds. In these structures, µ-EDTA acts as a pentadentate chelator for both terminal Cu centers within the centrosymmetric linear trinuclear anion. The Cu(µ-EDTA) chelates bind to the central Cu(Him)4 unit in subtly different ways: in compound 1, µ-EDTA has a free acetate arm and binds the central Cu(II) center through a syn,anti-carboxylate group. In contrast, in compound 2, the non-chelating acetate arm serves as a monodentate O-donor to the central Cu(II) atom, increasing the Cu(terminal)···Cu(central) distance from 6.08 Å in 1 to 6.80 Å in 2. Additionally, pairs of H2im+ ions in compound 2 display antiparallel π-stacking interactions. We conclude that the H2im+ counterions in compound 2 enable the magnetic isolation of the nearly identical trinuclear anion present in both compounds. DFT calculations further support the role of different interactions in stabilizing each crystal structure. In compound 2, dominant contributions from N–H···O hydrogen bonds and π-stacking interactions are accompanied by other, less conventional interactions, such as multiple C–H···O contacts and an O···CO(π-hole) interaction within the trinuclear anion. |
| publishDate |
2024 |
| dc.date.none.fl_str_mv |
2024 2025 2025 2025 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10261/375464 |
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http://hdl.handle.net/10261/375464 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-115637GB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-148453NB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-151538NB-I00 The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI https://doi.org/10.3390/ijms252313130 https://doi.org/10.3390/ijms252313130 Sí |
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info:eu-repo/semantics/openAccess |
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openAccess |
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application/pdf |
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Multidisciplinary Digital Publishing Institute |
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Multidisciplinary Digital Publishing Institute |
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reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC instname:Consejo Superior de Investigaciones Científicas (CSIC) |
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Consejo Superior de Investigaciones Científicas (CSIC) |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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