Dlf complexes with uniform coordination geometry: structural and magnetic properties of an LnNi2 core supported by a heptadentate amine phenol ligand.
The synthesis and physical characterization of a series of lanthanide (Ln(III)) and nickel (Ni(II)) mixed trimetallic complexes with the heptadentate (N(4)O(3)) amine phenol ligand H(3)trn [tris(2'-hydroxybenzylaminoethyl)amine] has been accomplished in order to extend our understanding of how amine phenol ligands can be used to coaggregate d- and f-block metal ions and to investigate further the magnetic interaction between these ions. The one-pot reaction in methanol of stoichiometric amounts of H(3)trn with NiX(2).6H(2)O (X = ClO(4), NO(3)) followed by addition of the corresponding LnX(3).6H(2)O salt, and then base, produces complexes of the general formula [LnNi(2)(trn)(2)]X.nH(2)O. The complexes were characterized by a variety of analytical techniques. Crystals of five of the complexes were grown from methanol solutions and their structures were determined by X-ray analysis: [PrNi(2)(trn)(2)(CH(3)OH)]ClO(4).4CH(3)OH.H(2)O, [SmNi(2)(trn)(2)(CH(3)OH)]NO(3).4CH(3)OH.2H(2)O, [TbNi(2)(trn)(2)(CH(3)OH)]NO(3).4CH(3)OH.3H(2)O, [ErNi(2)(trn)(2)(CH(3)OH)]NO(3).6CH(3)OH, and [LuNi(2)(trn)(2)(CH(3)OH)]NO(3).4.5CH(3)OH.1.5H(2)O. The [LnNi(2)(trn)(2)(CH(3)OH)](+) complex cation consists of two octahedral Ni(II) ions, each of which is encapsulated by the ligand trn(3)(-) in an N(4)O(2) coordination sphere with one phenolate O atom not bound to Ni(II). Each [Ni(trn)](-) unit acts as a tridentate ligand toward the Ln(III) ion via two bridging and one nonbridging phenolate donors. Remarkably, in all of the structurally characterized complexes, Ln(III) is seven-coordinate and has a flattened pentagonal bipyramidal geometry. Such uniform coordination behavior along the whole lanthanide series is rare and can perhaps be attributed to a mismatch between the geometric requirements of the bridging and nonbridging phenolate donors. Magnetic studies indicate that ferromagnetic exchange occurs in the Ni(II)/Ln(II) complexes where Ln = Gd, Tb, Dy, Ho, or Er.
Bayly
Simon R
SR
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada.
Xu
Zhiquiang
Z
Patrick
Brian O
BO
Rettig
Steven J
SJ
Pink
Maren
M
Thompson
Robert C
RC
Orvig
Chris
C