Abstract
Three novel metal-organic hosts with POM guests coordination polymers, [Co(bim)4][HPMoVI10VIV4O42] (1), {[Co(bim)2(H2O)]2 [PMoVI8VIVVV3O40(VIVO)2]}·2H2O (2), and {[Ni(bim)2(H2O)]2 [PMoVI8VIVVV3O40(VIVO)2]}□8H2O (3) (bim = bis (1-imidazolyl) methane) have been successfully prepared under hydrothermal conditions. Compound 1 shows one dimensional chain with bi-capping Keggin anion [HPMoVI10VIV4O42]2- (abbreviated as PMo10V4) as guest molecule, which forms a three dimensional array by hydrogen bonds. Considering that there are a large number of free coordinating N present on the organic ligand in 1, we increased the ratio of Co2+/bim and got a new polyoxometalate-based complex 2. Compound 2 mainly consists of host two dimensional rigid MOF sheets and guest bi-capping Keggin anion [PMoVI8 VIVVV3O40(VIVO)2]4- (denoted as PMo8V6) cluster, which are covalently-linked together to form a three dimensional array. Compound 3 and 2 are isomorphic, but contains the metal ions Ni2+ instead of Co2+ and the number of free water is different. Magnetothermal studies indicate that compound 1 and 2 all have antiferromagnetic interactions. Interestingly, compound 2 represents the novel 3D host-guest coordination polymer network with a gradual and partial spin-crossover phenomenon.
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