2026-04-28T21:05:33Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/75382023-04-18T11:15:39Zcom_10259_4363com_10259_5086com_10259_2604com_10259_3596col_10259_4364col_10259_3597

Thiosemicarbazonecopper/Halido Systems: Structure and DFT Analysis of the Magnetic Coupling Jiménez Pérez, Alondra Marcos-Gómez, Sara Madariaga, Gotzon Zapico, Manuel Vitoria, Pablo Tercero, Javier Torres, M. Begoña Lezama, Luis Cuevas Vicario, José Vicente Etxebarria, Íñigo García Tojal, Javier Chloro Coordination chemistry Copper Density functional theory Iodo Structure Thiosemicarbazone Bioquímica Química inorgánica Biochemistry Chemistry, Inorganic Experimental magnetic studies performed on the [{CuLX}2 ] system (HL = pyridine-2- carbaldehyde thiosemicarbazone, X = Cl−, Br−, I−) point to the larger electronegativity in X, the lower magnitude of the antiferromagnetic interactions. In order to confirm this and other trends observed and to dip into them, computational studies on the [{CuLX}2 ] (X = Cl− (1), I− (2)) compounds are here reported. The chemical and structural comparisons have been extended to the compounds obtained in acid medium. In this regard, chlorido ligands yield the [Cu(HL)Cl2 ]·H2O (3) complex, whose crystal structure shows that thiosemicarbazone links as a tridentate chelate ligand to square pyramidal Cu(II) ions. On the other hand, iodido ligands provoke the formation of the [{Cu(H2L)I2 }2 ] (4) derivative, which contains pyridine-protonated cationic H2L + as a S-donor monodentate ligand bonded to Cu(I) ions. Crystallographic, infrared and electron paramagnetic resonance spectroscopic results are discussed. Computational calculations predict a greater stability for the chlorido species, containing both the neutral (HL) and anionic (L−) ligand. The theoretical magnetic studies considering isolated dimeric entities reproduce the sign and magnitude of the antiferromagnetism in 1, but no good agreement is found for compound 2. The sensitivity to the basis set and the presence of interdimer magnetic interactions are debated. This research was funded by the European Union H2020-LC-SC3-2020-NZE-RES-CC, NMBP-16-2020-GA 953152 and DT-NMBP-04-2020 Projects, together with the Ministerio de Ciencia, Innovación y Universidades CTQ(QMC) RED2018-102471-T MultiMetDrugs Network (Spain), PGC2018-093745-B-I00 and PID2019-111215RB-100, Consejería de Educación of Junta de Castilla y León and FEDER BU049P20 and FUNDACION BANCARIA CAIXA D. ESTALVIS I PENSIONS DE BARCELONA 001. Ministerio de Ciencia e Innovación PID2019-106644GB-I00 and Gobierno Vasco IT1458-22. 2023-03-13T12:16:13Z 2023-03-13T12:16:13Z 2023-01 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://hdl.handle.net/10259/7538 10.3390/inorganics11010031 2304-6740 eng Inorganics. 2023, V. 11, n. 1, 31 https://doi.org/10.3390/inorganics11010031 info:eu-repo/grantAgreement/EC/H2020/953152/EU/Development and scaled Implementation of sAfe by design tools and Guidelines for multicOmponent aNd hArn nanomateriaLs/DIAGONAL/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102471-T/ES/METALOFARMACOS MULTIFUNCIONALES PARA DIAGNOSIS Y TERAPIA/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-093745-B-I00/ES/ESTUDIO DE PRIMEROS PRINCIPIOS DE LAS PROPIEDADES ESTRUCTURALES Y ELECTRONICAS DE NANOMATERIALES Y SU REACTIVIDAD EN EL CONTEXTO DE VARIAS AREAS TECNOLOGICAS/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-111215RB-I00/ES/DESARROLLO DE NUEVOS SENSORES QUIMICOS PARA LA DETECCION RAPIDA Y SELECTIVA DE DISPOSITIVOS EXPLOSIVOS IMPROVISADOS/ info:eu-repo/grantAgreement/Junta de Castilla y León//BU049P20//Estrategias sintéticas sostenibles para la halogenación directa de nitrocompuestos y la preparación de electrolitos orgánicos para baterías de flujo redox/ info:eu-repo/grantAgreement/Fundación Bancaria Caixa d'Estalvis i Pensions de Barcelona//2020%2F00062%2F001/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106644GB-I00/ES/ESTRUCTURA Y PROPIEDADES FISICAS DE MATERIALES TOPOLOGICOS Y MATERIALES MAGNETICOS/ info:eu-repo/grantAgreement/Gobierno Vasco//IT1458-22/ Atribución 4.0 Internacional http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess application/pdf MDPI