Tcne Rare Earth Complexes Synthesis, Characterization And Performance Study

Reactions of LnCl3·4THF with LiTCNE (TCNE = tetracyanoethylene) yielded 1-3 under nitrogen using standard Schlenk techniques in this paper. These complexes were characterized by melting point, IR spectrum, Ultraviolet-Visible, element analysis and Thermal gravimetric analysis, and their structures can be described as Ln2[C4(CN)8]3·(THF)6 (Ln = Sm (1), Gd (2) and Er (3)). Each Ln(III) ion is in a nine coordination geometry bounded by six [C4(CN)8]2- and three THF molecules.Meanwhile, five new 3d-4f heterobinuclear Schiff base (L1 = N,N'- ethylenebis(salicylideneimine), L2 = N,N'-bis(2-hydroxy-3-methoxybenzylidene)-1,3- diaminopropane)) LiTCNE complexes 4-8: {[L1Cu]Gd(NO3)Cu2(CN)4}·MeOH (4), {[L2Cu]Gd(NO3)Cu2(CN)4}·MeOH (5), {[L2Ni(MeOH)2]Gd(NO3)Ni2(CN)4}·MeOH (6), {[L2Zn(NO3)]Gd(NO3)Zn2(CN)4}·MeOH(7)&{[L2Co(CH3COO)2]GdCo2(CN)4}·MeOH (8) have been synthesized. Complexes 4 have been structurally characterized by single-crystal X-ray crystallographic analysis. In complex 4, each Gd(III) ion, showing a nine-coordinated tricapped trigonal prismatic geometry. The deoxidization of CuII by LiTCNE forms TCNE and CuI. Furthermore, CuI, CNˉand L1CuIIGd react self-assembly at mild condition to provide a complex 4. Each copper positive ion has different price, the copper in L1CuIIGd ligand is Cu2+, and the copper in chain is Cu1+. Complexes 5-8 were characterized by melting point, IR spectrum, Ultraviolet-Visible, element analysis and Thermal gravimetric analysis, and their structures were similar to complex 4.The electrochemical properties of 4-8 have been investigated by cyclic voltammetry in acetonitrile solution of tetra-n-butylammonium hexafluorophosphate. On the negative scan, the cyclic voltammogram of 4-8 show quasi-reversible one-electron reduction. On the positive scan, the cyclic voltammogram of 4-8 shows one irreversible one-electron oxidation. Conductivity measurements show that complexes behaved as weak electrolytes in CH3CN.The variable-temperature magnetic properties of 4 have been investigated over the temperature 2-300 K at 5000 Oe. The complex 4 shows a weak ferromagnetic interaction between Cu(II)-Gd(III) ions.