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Linker stoichiometry-controlled stepwise supramolecular growth of a flexible Cu2Tb single molecule magnet from monomer to dimer to one-dimensional Chain
Published in American Chemical Society
Volume: 14
Issue: 5
Pages: 2588 - 2598
A trinuclear complex [(CuL)2Tb(H2O)(NO 3)3]·MeOH·H2O (1) is synthesized by using a metalloligand [CuL] (H2L = N,N′-bis(salicylidene)-1, 3-propanediamine or salpn). This complex is used as a new 3d-4f metallatecton for stepwise supramolecular oligomerization along with a simple diimine linker, 4,4′-bipyridine (bpy). A ratio of metallatecton/linker = 2:1 is conducive for the formation of a dimer [{(CuL)2Tb(H2O)(NO 3)3}2bpy]·2MeOH·4H2O (2), whereas a higher proportion of linker at a ratio of 1:1 gives rise to a zigzag one-dimensional coordination polymer {[(CuL)2Tb(NO 3)3bpy]·MeOH·2H2O} ∞ (3). The inherent conformational flexibility of the trinuclear (CuL)2Tb node which is folded (cisoid) for 1 and 2 (asymmetric TbO9 tricapped trigonal prism) and unfolded (transoid) for 3 (a C2-symmetric TbO10 tetradecahedron) seems to stabilize the crystal packing of these coordination-driven self-assemblies. The rapidly saturated magnetization at 1.8 K for 1 (11 μB) and 2 (22 μB) clearly indicates the presence of Tb-Cu ferromagnetic coupling through the phenoxido bridges of the Cu(μ1,1-O) 2Tb(μ1,1-O)2Cu cores. A slow saturation behavior has been found for 3 (9.5 μB). Both in-phase and out-of-phase ac magnetic measurements of 1 under an applied dc magnetic field reveal temperature dependence of the susceptibility at different frequencies below 5 K, characteristic of single molecule magnets (SMMs), which is conserved in 2 and 3 signifying oligo- and polymeric aggregates of SMMs. © 2014 American Chemical Society.
About the journal
JournalData powered by TypesetCrystal Growth and Design
PublisherData powered by TypesetAmerican Chemical Society
Open AccessNo