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  • Title: Influence of the central metal ion in controlling the self-assembly and magnetic properties of 2D coordination polymers derived from [(NiL)2M](2+) nodes (M = Ni, Zn and Cd) (H2L = salen-type di-Schiff base) and dicyanamide spacers.
    Author: Das LK, Gómez-García CJ, Ghosh A.
    Journal: Dalton Trans; 2015 Jan 21; 44(3):1292-302. PubMed ID: 25418864.
    Abstract:
    Three new 2D coordination polymers (CPs) (2)∞[(NiL)2Ni(μ1,5-N(CN)2)2]n (), (2)∞[(NiL)2Cd(μ1,5-N(CN)2)2]n () and (2)∞[(NiL)2Zn(μ1,5-N(CN)2)2]n () have been synthesized by reacting a [NiL] "metalloligand" (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) with three different metal(ii) (Ni, Cd and Zn) perchlorates and sodium dicyanamide, with identical molar ratios of the reactants. All three products have been characterized by IR and UV-Vis spectroscopies, elemental analyses, powder and single crystal X-ray diffraction and variable temperature magnetic measurements. The isomorphous compounds and consist of similar [(NiL)2M(μ1,5-N(CN)2)] (M = Ni for and Cd for ) angular trinuclear units in which two terminal "metalloligands" [NiL] coordinate to the central nickel(ii) (in ) or cadmium(ii) (in ) ion through phenoxido oxygen atoms. The μ1,5-bridging dicyanamido spacers connect the central Ni(ii) or Cd(ii) of one node to terminal Ni(ii) of two different nodes giving rise to 2D CPs. Compound also contains trinuclear units with the same formula as those of and : [(NiL)2M(μ1,5-N(CN)2)] (M = Zn in ). The main differences are that these units are linear in and the dicyanamide spacers link only the nickel atoms of neighbouring nodes. As in and , these trinuclear units are connected to four other units via four μ1,5-bridging dicyanamido ligands, giving rise to 2D CP with a similar topology: a uninodal 4-connected underlying net with the sql (Shubnikov tetragonal plane net) topology and (4(4)·6(2)) point symbol. The magnetic properties show the presence of moderate intra-trimer antiferromagnetic interactions in (J = -12.9 cm(-1)) and weak antiferromagnetic interactions between the terminal Ni(ii) ions in (J = -2.4 cm(-1)). In the Ni(ii) ions are well isolated by the central Zn(ii) ion and accordingly, only a very weak antiferromagnetic interaction through the single μ1,5-bridging dicyanamido ligands is observed (J = -0.44 cm(-1), D = -3.9 cm(-1)).
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