Two-Dimensional Coordination Polymers Constructed by [NiIILnIII] Nodes and [WIV(bpy)(CN)₆]2– Spacers: A Network of [NiIIDyIII] Single Molecule Magnets

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Abstract

Three isomorphous two-dimensional (2D) coordination polymers of general formula {[Ni(II)(valpn)Ln(III)(NO3)(H2O)(μ-NC)4W(IV)(bipy)(CN)2]·xH2O·yCH3CN}n have been synthesized by reacting Ph4P[W(V)(CN)6(bipy)] with the heterodinuclear [Ni(II)Ln(III)(valpn)(O2NO)3] complexes [H2valpn = 1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol), bipy = 2,2'-bipyridine, and Ln = Gd (1), Dy (2), and Tb (3) with x = 2 (1), 3.9 (2), and 3.35 (3) and y = 2.50 (1), 2 (2), and 1.8 (3)]. Their crystal structures consist of [Ni(II)Ln(III)] 3d-4f nodes which are connected by [W(IV)(bipy)(CN)6](2-) diamagnetic linkers resulting from the reduction of W(V) to W(IV) during the reaction process. The Ni(II) and Ln(III) ions occupy the inner and outer coordination sites of the dideprotonated valpn ligand, respectively, and they are doubly bridged by the phenoxo oxygen atoms of such a ligand. The value of Ni(II)···Ln(III) separation through this bridge is 3.4919(10) (1), 3.4760(10) (2), and 3.4799(9) (3) Å, and those of the angles at the bridgehead phenoxo atoms are 106.6(2) and 107.3(2) (1), 106.9(2), and 107.8(2) (2) and 106.5(2)-106.8(2)° (3). Each W(IV) is eight-coordinated with a bidentate bipy molecule and six cyanide-carbon atoms building a somewhat distorted square antiprism environment. The rare-earth cations are nine-coordinated, the donor atoms describing a monocapped square antiprism for 1 and 3 and a tricapped trigonal prism for 2. Magnetic susceptibility measurements in the temperature range 1.9-300 K show the occurrence of ferromagnetic interactions between the Ni(II) and Ln(III) ions in 1-3. Frequency-dependent alternating susceptibility signals were observed for the Dy(III) derivative below 8.0 K under an applied dc field of 2500 G indicating the presence of slow magnetic relaxation with values of the pre-exponential factor (τ0) and energy barrier (E(#)) of ca. 5.7 × 10(-8) s and 15.9 cm(-1), respectively. Complex 2 constitutes the first example of a 2D 3d-4f heterobimetallic single molecule magnet (SMM).

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