RT info:eu-repo/semantics/article
T1 Thiosemicarbazonecopper/Halido Systems: Structure and DFT Analysis of the Magnetic Coupling
A1 Jiménez Pérez, Alondra
A1 Marcos-Gómez, Sara
A1 Madariaga, Gotzon
A1 Zapico, Manuel
A1 Vitoria, Pablo
A1 Tercero, Javier
A1 Torres, M. Begoña
A1 Lezama, Luis
A1 Cuevas Vicario, José Vicente
A1 Etxebarria, Íñigo
A1 García Tojal, Javier
K1 Chloro
K1 Coordination chemistry
K1 Copper
K1 Density functional theory
K1 Iodo
K1 Structure
K1 Thiosemicarbazone
K1 Bioquímica
K1 Biochemistry
K1 Química inorgánica
K1 Chemistry, Inorganic
AB 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 lowermagnitude of the antiferromagnetic interactions. In order to confirm this and other trends observedand to dip into them, computational studies on the [{CuLX}2] (X = Cl− (1), I− (2)) compounds are herereported. The chemical and structural comparisons have been extended to the compounds obtained inacid medium. In this regard, chlorido ligands yield the [Cu(HL)Cl2]·H2O (3) complex, whose crystalstructure 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 toCu(I) ions. Crystallographic, infrared and electron paramagnetic resonance spectroscopic results arediscussed. Computational calculations predict a greater stability for the chlorido species, containingboth the neutral (HL) and anionic (L−) ligand. The theoretical magnetic studies considering isolateddimeric entities reproduce the sign and magnitude of the antiferromagnetism in 1, but no goodagreement is found for compound 2. The sensitivity to the basis set and the presence of interdimermagnetic interactions are debated.
PB MDPI
YR 2023
FD 2023-01
LK http://hdl.handle.net/10259/7538
UL http://hdl.handle.net/10259/7538
LA eng
NO 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.
DS Repositorio Institucional de la Universidad de Burgos
RD 29-abr-2024