Cyano-bridged Metal Complexes Synthesis, Crystal Structure And Magnetic Properties

Self-assembly of the cyanometalate precursor with the fully solvated species[A(H20)6]^a+ or coordinatively unsaturated metal complexes [A(L)(H₂O)_x]^(a-1)+,affords eight new cyano-bridged bimetallic complexes, which were characterized structurelly and magnetically.1.Reaction of tailored tetracyanometalate iron(Ⅲ) precursors of [Fe(bipy)(CN)₄]^- with manganese(Ⅲ) Schiff bases complexes of [Mn(salen)]^-and[Mn(salpn)]^-(salen=N,N'-ethylenebi(salicylicdeneiminato) dianion,salpn=N,N'-propylenebis(salicylideneiminato)dianion) obtained two cyano-bridged Mn(Ⅲ)-Fe(Ⅲ) bimetallic chain assemblies of[Mn(salen)][Fe(bipy)(CN)₄](1) and[Mn(salpn)][Fe(bipy)(CN)₄](2). Similarly,a trinuclear Ni(Ⅱ)-Fe(Ⅲ) compound[Ni(teta)][Fe(phen)(CN)₄]₂·4CH₃OH(3) was obtained by assembly of[Fe(phen)(CN)₄]^-and a macrocyclic Ni(Ⅱ) complex Ni(teta)^2-(teta=5,7,12,14,14-hexamethyl-1, 4,8,11-tetraazacyclotetradeca).2.Two ladder-like one-dimensional chain complexes of[{Fe^Ⅱ(bipy)(CN)4}-{Nd^Ⅲ(NO₃)(CH₃OH)₃}]₄·4CH₃OH·2H₂O(4) and[Fe^Ⅱ(bipy)(CN)₄][Y^Ⅲ-(NO₃)(CH₃OH)₃]·CH₃OH(5) were synthesized by reaction of tailored tetracyanometalate iron(Ⅱ)precursor of[Fe(boipy)(CN)₄]^2- with lanthanide metal ions.3.Self-assembly of pentacyano-nitroprusside anion of[Fe(CN)₅NO]^2- and Mn^Ⅲ-Schiff bases complex of[Mn(salen)H₂O]⁺ affords a twodimensional cyano-bridged bimetallic compound[Mn(salen)]₂[Fe(CN)₅-(NO)]·2H₂O(6).4.Reaction of hexacyanometalate[M(CN)₆]^3-(M=Fe^Ⅲ,Cr^Ⅲ) with[CuL⁴-ClO₄)₂ (L⁴=3,10-dibutyl-1,3,5,8,10,12-hexaazacyclotetradecane) produces two cyano-bridged compounds of[CuL⁴]₃[Fe(CN)₆]₂·2H₂O(7) and {[CuL⁴]₃[Cr(CN)₆]₂}·4CH₃OH·4H₂O(8).Complex 7 has two distinct neutral moieties,one is a 2D polymeric layer,the other is a discrete Cu₃Fe₂ pentanuclear chain-like unit.Complex 8 shows a 1D zigzag chain structure.These complexes have been characterized by elemental analyses,ICP,IR, TG-DSC and X-ray single-crystal diffraction.Magnetic properties of complexes 1,2,6,7,8 have been measured by means of variable-temperature magnetic susceptibility and the magneto-structural correlations have been explored.