title: Molecular architectures for trimetallic d/f/d complexes: structural and magnetic properties of a LnNi2 core.
abstract: A series of cationic, trimetallic d/f/d complexes have been prepared which use a multidentate, macrocyclic amine phenol ligand to coordinate divalent first row d-block transition metal ions (TM) and lanthanides (Ln) ions in close proximity, desirable for magnetic studies. Isolable complexes of the d/f/d cluster compounds with the formula [Ln(TM)2(bcn)2]ClO4.nH2O, where H3bcn is tris-N, N', N''-(2-hydroxybenzyl)-1,4,7-triazacyclononane, TM = Zn(II) and Ni(II) and Ln = La(III), Nd(III), Gd(III), Dy(III), and Yb(III), were synthesized by a one-pot sequential reaction of stoichiometric amounts of H 3bcn with the TM(II) and Ln(III) metal ions. The spontaneously formed cationic complexes were characterized by a variety of analytical techniques including IR, NMR, +ESI-MS, and EA. The [TM(Hbcn)].nH2O and [TM3(bcn)2].nH2O complexes were also synthesized to probe the building blocks of the d/f/d coaggregated species. The solid-state X-ray crystal structures of [GdNi2(bcn)2(CH3CN)2]ClO4.CH3CN and [GdZn2(bcn)2(CH3CN)2]ClO4.CH3CN were determined to be nearly identical with each TM(II) encapsulated in an octahedral geometry by the N3O3 binding pocket of the bcn (3-) ligand. The eight coordinate Gd(III) was bicapped by two [TM(bcn)](-) moieties and coordinated by two solvent molecules. Because of the isostructurality of the [LnZn2(bcn)2]ClO4.nH2O and [LnNi2(bcn)2]ClO4.nH2O complexes, an empirical approach using the LnZn2 magnetic data was utilized to remove first-order anisotropic contributions from the LnNi2 species. Ferromagnetic spin interactions were determined for the [LnNi2(bcn)2]ClO4.nH2O complexes, where Ln = Gd(III), Dy(III), and Yb(III), while an antiferromagnetic exchange was observed for Ln = Nd(III).
authors.affiliation: Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Cheri A
authors.initials: CA
authors.lastname: Barta
authors.forename: Simon R
authors.initials: SR
authors.lastname: Bayly
authors.forename: Paul W
authors.initials: PW
authors.lastname: Read
authors.forename: Brian O
authors.initials: BO
authors.lastname: Patrick
authors.forename: Robert C
authors.initials: RC
authors.lastname: Thompson
authors.forename: Chris
authors.initials: C
authors.lastname: Orvig