Repozytorium

Synthesis, characterization, and magnetic properties of a series of copper(II) chloride complexes of pyridyliminebenzoic acids.

Autorzy

Elena A. Buvaylo

Vladimir N. Kokozay

Valeriya G. Makhankova

Andrii K. Melnyk

Maria Korabik

Maciej Witwicki

Brian W. Skelton

Olga Yu. Vassilyeva

Rok wydania

2018

Czasopismo

European Journal of Inorganic Chemistry

Strony

1603-1619

DOI

10.1002/ejic.201701391

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

A series of CuII halide complexes, Cu(HL1)Cl2·CH3OH (1), [Cu(L1)Cl]2·H2O (2), [Cu(HL2)Cl2]2·2DMF (3), [Cu(HL2)2Cl]nCln·2nH2O (4), and [Cu(L3)Cl]n (5), containing pyridyliminebenzoic acids HL1, HL2, and HL3 derived from o‐, m‐, and p‐aminobenzoic acids, respectively, have been obtained as single crystals and characterized by elemental analysis, IR, EPR spectroscopy, magnetic measurements, and single‐crystal X‐ray diffraction techniques. The results obtained show the formation of molecular (1), dimeric (2, 3), and polymeric structures (4, 5) based on chloride (14) and carboxylate bridges (5) with copper(II) ions in the square pyramidal geometry of varying degrees of distortion. In the case of 2 and 5 the ligand deprotonation was completely achieved even in the absence of a base. The closest Cu···Cu separations are found in the crystal lattices of the polymer 5 (3.33 Å) and dimers 2 (3.35 Å) and 3 (3.38 Å). The X‐band polycrystalline EPR spectra of 13 with typical axial patterns show no indication of exchange interactions between copper ions in the range 295–77 K. The observed rhombic features of the EPR spectra of 4 arise from the coupling of g‐tensors from differently oriented CuII coordination polyhedra in the solid state. A characteristic spin‐triplet EPR spectrum of 5 at 77 K was simulated by using the spin‐Hamiltonian parameters for S = 1, gx = 2.08, gy = 2.11, gz = 2.37 and the value of the zero‐field splitting parameter D of 0.137 cm–1. Magnetic susceptibility measurements revealed antiferromagnetic (13, 5) and ferromagnetic coupling (4) between the metal atoms at low temperatures. Theoretical methods were employed to provide additional insight into magnetic interactions in the studied compounds.

Słowa kluczowe

Copper, N,O ligands, Aminobenzoic acids, schiff bases, X-ray diffraction, structure elucidation, magnetic properties, density functional calculations

Adres publiczny

https://doi.org/10.1002/ejic.201701391

Strona internetowa wydawcy

onlinelibrary.wiley.com

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