Magnatic Interactions in the Coper Complex (L-Aspartato)(1,10-phenanthroline)copper(II) Hydrate. An Exchange-Coupled Extended System with Two Dissimilar Copper Ions

Brondino C.D.; Calvo R.; Atria A.M.; Spodine, E.; Nascimento O.R.; Pene O.

Abstract

We report EPR measurements in single-crystal samples at the microwave frequencies 9.8 and 34.3 GHf and magnetic susceptibility measurements in polycrystalline samples for the ternary complex of copper with aspartic acid and phenanthmline. (L-aspartato)( 1, 10-phenanthmline)copper(II) hydrate. The crystal lattice of this compound is composed of two dissimilar copper ions identified and Cu(A) and Cu(B), which are in two types of copper chains called A and B, respectïvely, running parallel to the b crystal axis. The copper ions in the A chains are connected by the aspartic acid molecule, and those in the B chains by a chemical path that involves a carboxylate bridge and a hydrogen bond. Both chains are held together by a complex network of hydrogen bonds and by hydrophobic interactions between aromatic amines. Magnetic susceptibility data indicate a Curie-Weiss behavior in the studied temperature range (2-300 K). The EPR spectra at 9.8 GHz display a single exchange collapsed resonance for any magnetic field orientation, in the so-called strong exchange regime. Those at 34.3 GHz are within the so-called weak exchange regime and display two resonances which belong to each type of copper ion chain. The decoupling of the spectra at 34.3 GHz using a theory based on Andersen's model for the case of two weakly exchange coupled spins S = 1/2 allows one to obtain the angular variation of the squares of the g-factor and the peak-to-peak line width of each resonance. This model also allows one to evaluate the exchange parameter |J AB|K| = 2.7(6) mK. associated with the chemical path connecting dissimilar copper ions. The line width data obtained for each component of the spectra at 34.3 GHz are analyzed in terms of a model based on Kubo and Tomita's theory, to obtain the exchange parameters |J A|K| = 0.77(2) K and |J B|K| = 1.44(2) K associated with the chemical paths connecting the similar copper ions of types A and B, respectively.

Más información

Título de la Revista: INORGANIC CHEMISTRY
Volumen: 36
Número: 14
Editorial: American Chemical Society
Fecha de publicación: 1997
Página de inicio: 3183
Página final: 3189
URL: http://www.scopus.com/inward/record.url?eid=2-s2.0-0000680662&partnerID=q2rCbXpz