Thiosemicarbazonecopper/Halido Systems: Structure and DFT Analysis of the Magnetic Coupling

Experimental magnetic studies performed on the [{CuLX}2] system (HL = pyridine-2-carbaldehyde thiosemicarbazone, X Cl−, Br−, I−) point to larger electronegativity in X, lower magnitude of antiferromagnetic interactions. In order confirm this and other trends observed dip into them, computational (X Cl− (1), I− (2)) compounds are here reported. The chemical structural comparisons have been extended obtained acid medium. regard, chlorido ligands yield [Cu(HL)Cl2]∙H2O (3) complex, whose crystal structure shows that thiosemicarbazone links as a tridentate chelate ligand square pyramidal Cu(II) ions. On hand, iodido provoke formation [{Cu(H2L)I2}2] (4) derivative, which contains pyridine-protonated cationic H2L+ S-donor monodentate bonded Cu(I) Crystallographic, infrared electron paramagnetic resonance spectroscopic results discussed. Computational calculations predict greater stability for species, containing both neutral (HL) anionic (L−) ligand. theoretical considering isolated dimeric entities reproduce sign antiferromagnetism 1, but no good agreement is found compound 2. sensitivity basis set presence interdimer interactions debated.