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This work reports our first results in the area of the reactivity of coordinated chloroximes. The 1:2:2:2 Zn(NO₃)₂∙6H₂O/Eu(NO₃)₃∙6H₂O/ClpaoH/Et₃N reaction mixture in MeOH, where ClpaoH is pyridine-2-chloroxime, resulted in complex [ZnCl₂(L)] (1); L is the di(2-pyridyl)furoxan [3,4-di(2-pyridyl)-1,2,5-oxadiazole-2-oxide] ligand. The same complex can be isolated in the absence of the lanthanoid. The direct reaction of ZnCl₂ and pre-synthesized L in MeOH also provides access to 1. In the tetrahedral complex, L behaves as a N_pyridyl,N′_pyridyl-bidentate ligand, forming an unusual seven-membered chelating ring. The Hirshfeld Surface analysis of the crystal structure reveals a multitude of intermolecular interactions, which generate an interesting 3D architecture. The complex has been characterized by FTIR and Raman spectroscopies. The structure of 1 is not retained in DMSO (dimethylsulfoxide) solution, as proven by NMR (¹H, ¹³C, ¹⁵N) spectroscopy and its molar conductivity value. Upon excitation at 375 nm, solid 1 emits blue light with a maximum at 452 nm; the emission is of an intraligand character. The geometric and energetic profiles of possible pathways involved in the reaction of ClpaoH and Zn(NO₃)₂∙6H₂O in MeOH in the presence of Et₃N has been investigated by DFT (Density Functional Theory) computational methodologies at the PBE0/Def2-TZVP(Cr)∪6-31G(d,p)(E)/Polarizable Continuum Model (PCM) level of theory. This study reveals an unprecedented cross-coupling reaction between two coordinated 2-pyridyl nitrile oxide ligands. Full article