Structures, magnetic properties, and XPS of cyanide-bridged NdIII/SmIII/GdIII–CrIII complexes

Synthesis, structural characterization, and spectroscopic and magnetic properties of three new cyano-bridged 3d–4f bimetallic complexes, LnIII(DMF)4(H2O)3CrIII (CN)6 · nH2O (Ln = Nd, Sm, Gd), have been described. The Nd–Cr complex crystallizes in the monoclinic P21/n space group with the following unit cell parameters: a = 20.063(7) Å, b = 8.967(4) Å, c = 18.023(6) Å, b = 96.12(3)°, V = 3224(2) Å3, and Z = 4. The neodymium (III) ion, which adopts anti-prism eight-coordination environment, is linked to the [CrIII(CN)6]3− moiety through a bridging cyanide ligand with Nd–N = 2.550(4) Å and Nd–N–C = 164.4(4)°. The variable-temperature (0.5 T at 2–300 K) and variable-field (0–5 T at 2 and 5 K) magnetic measurements reveal that the weak interaction of Gd–Cr complexes differs from that of Nd–Cr and Sm–Cr ones mainly because of the lack of orbital angular momentum. The XPS and diffuse reflectance electronic spectra were also measured to discuss charge transfer transitions concerning π-backdonation from the viewpoint of magneto-optical functions.

Crystal structures, magnetic properties, and electronic and X-ray photoelectron spectra of dinuclear clusters of LnIII(DMF)4(H2O)3CrIII(CN)6 · nH2O (LnIII = NdIII, SmIII, GdIII) have been discussed in view of structures and magneto-optical correlations.Figure optionsDownload as PowerPoint slide