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Bi‐Compartmental Schiff‐Base with Peripheral Ester Functionalization: Synthesis and Magnetic Behavior of Bimetallic Zn‐Ln Complexes (Ln = Dy, Tb, Gd)
Author(s) -
Béreau Virginie,
Bolvin Hélène,
Duhayon Carine,
Sutter JeanPascal
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600924
Subject(s) - chemistry , ligand (biochemistry) , schiff base , steric effects , bimetallic strip , lanthanide , reactivity (psychology) , coordination sphere , crystallography , crystal structure , stereochemistry , ion , metal , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
A novel ester‐functionalized bi‐compartmental Schiff‐base ligand and its dinuclear Zn‐Ln complexes [Ln = Dy ( 1 ), Tb ( 2 ), Gd ( 3 )] are reported herein. Athough electron‐withdrawing substituents at the para position of the phenol moieties do not change the coordination environment of the Ln centers in comparison with the nonfunctionalized ligand, they have a clear steric effect on the crystal packing and alter the coordination strength of the central ligand core. This is illustrated by the atypical reactivity of the bi‐compartmental Schiff‐base ligand towards Ln coordination and corroborated by its longer bond lengths to the rare‐earth ions in comparison with the nonfunctionalized ligand. Crystal structures, magnetic behavior, and ab initio calculations for the two series of complexes are reported. A slow relaxation of the magnetization with an energy barrier of 96 K was found for Dy derivative 1 in zero field.