Enhancing the Magnetization Blocking Energy of Biradical-Metal System by Merging Discrete Complexes into One-Dimensional Chains

The reaction of nitronyl nitroxide biradical NITPhMeImbis [5-(2-methylimidazole)-1,3-bis(1-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)-benzene] with Ln(hfac)(3) center dot 2H(2)O and Cu(hfac)(2) (hfac=hexafluoroacetylacetonate), led to two series of 2p-3d-4f complexes, namely, nona-spin clusters, [Ln(2)Cu(3)(hfac)(12)(NITPhMeImbis)(2)] (Ln=Gd 1, Dy 2), or one-dimensional chains [LnCu(2)(hfac)(7)(NITPhMeImbis)] (Ln=Y 3, Dy 4, Tb 5) depending on the temperature of the reaction. All five complexes contain a biradical-Ln unit in which the biradical chelates the Ln(III) ion by the means of one aminoxyl (i. e. NO) group of each NIT unit. For the discrete complexes, a Cu(hfac)(2) links two biradical-Ln units via one of the remaining NO groups, while for the chain compounds, the two remaining NO groups of the biradical-Ln moiety are each coordinated to a Cu(hfac)(2) unit to form a 1D coordination polymer. Moreover, a terminal Cu(hfac)(2) unit is coordinated to the imidazole-N atom of the NITPhMeImbis ligand. Spin dynamics investigations evidenced the onset of slow relaxation of the magnetization for 2, whereas 4 and 5 exhibit a typical single-chain magnet behavior. This highlights the vital role of the 1D spin correlation in the blocking of the magnetization. These results illustrate that from the same basic building blocks, magnetic relaxation can be carefully modulated by structural adjustments.

Automated summary

The reaction of nitronyl nitroxide biradical NITPhMeImbis with Ln(hfac)(3) center dot 2H(2)O and Cu(hfac)(2) led to the formation of two series of complexes, nona-spin clusters [Ln(2)Cu(3)(hfac)(12)(NITPhMeImbis)(2)] or one-dimensional chains [LnCu(2)(hfac)(7)(NITPhMeImbis)], depending on the reaction temperature. These complexes contain a biradical-Ln unit where the biradical chelates the Ln(III) ion with one aminoxyl group of each NIT unit. The complexes exhibit different magnetic behaviors, with some showing slow relaxation of magnetization and others exhibiting single-chain magnet behavior.