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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 Npyridyl,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.

inorganics

Reactivity of Coordinated 2-Pyridyl Oximes: Synthesis, Structure, Spectroscopic Characterization and Theoretical Studies of Dichlorodi{(2-Pyridyl)Furoxan}Zinc(II) Obtained from the Reaction between Zinc(II) Nitrate and Pyridine-2-Chloroxime