Design of one-dimensional coordination networks from a macrocyclic {3d-4f} single-molecule magnet precursor linked by [W(CN)8]3- anions.
The outcome of 1:1 reactions of the tetranuclear 3d-4f Single Molecule Magnet (SMM) [Cu3Tb(L(Pr))(NO3)2(H2O)]NO3 (1) with (TBA)3[W(CN)8] (TBA = tri-n-butyl ammonium cation, [(n-Bu)3N-H](+)) in dimethylformamide (DMF) is dependent on the crystallization method employed: liquid-liquid diffusion of the reagents together gives {[Cu3Tb(L(Pr))W(CN)8(DMF)4]·(DMF)}n (2) whereas diethyl ether vapor diffusion into the reaction solution gives {[Cu3Tb(L(Pr))W(CN)8(DMF)3(H2O)3]·(DMF)1.5·(H2O)0.5}n (3). Both compounds are obtained as black single crystals and feature one-dimensional (1D) coordination networks (chains) of [1](3+) macrocycles linked by [W(CN)8](3-) anions. The two assemblies differ from a structural point of view. Complex 2 has a stepped arrangement with the linkers bound to the opposite faces of the macrocycle, whereas 3 has a square-wave arrangement due to the linkers binding to the same face of the macrocycle. Both compounds display an antiferromagnetic ground state below 3.5 and 2.4 K with a metamagnetic and antiferromagnetic (T, H) phase diagram for 2 and 3, respectively. Remarkably the slow dynamics of the magnetization of the [1](3+) macrocycle units is preserved in 3 while this property is quenched in 2 because of stronger intra- and interchain magnetic interactions inducing a higher critical temperature.
Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago , P.O. Box 56, Dunedin 9054, New Zealand.
Sébastien
S
Dhers
Humphrey L C
HL
Feltham
Rodolphe
R
Clérac
Sally
S
Brooker