Articles written in Journal of Chemical Sciences

    • Cyanide- and phenoxo-bridged heterobimetallic Fe(III)-Mn(III) complexes: Synthesis, crystal structures and magnetic properties

      Daopeng Zhang Ping Wang Kexun Chen Xia Chen

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      By employing two $mer$-tricyanidoiron(III) precursors [Ph4P][FeIII(pcq)(CN)3] and [Ph4P][FeIII (pzq)(CN)3] as building blocks and a salen-tpye Schiff-basemanganese (III) compound as assembling segment, two tetranuclear cyanide- and phenoxo- bridged heterobimetallic Fe(III)-Mn(III) complexes {[Mn(saltmen)] [Fe(pcq)(CN)3]}2·2CH3OH (1) and {[Mn(saltmen)] [Fe(pzq)(CN)3]}2·2CH3OH (2) (pcq = 8-(pyridine-2-carboxamido, pzq = 8-(pyrazine-2-carboxamido, saltmen2− = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato) dianion) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single x-ray analysis reveals their isostructural cyanide-bridged Fe(III)-Mn(III) binuclear structure. The binuclear entity is self-complementary through phenoxo oxygen from the neighbouring complex, giving cyanide- and phenoxo- bridged tetranuclear structure. Furthermore, under the help of the intermolecular 𝜋-𝜋 interaction, these two complexes can be constructed into 1D infinite chain supramolecular structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Fe(III) and Mn(III) ions bridged by cyanide group with 𝐽 = 5.34 cm-1 and 5.55 cm-1 for complexes 1 and 2, respectively.

    • Polynuclear and one-dimensional cyanide-bridged heterobimetallic complexes: synthesis, crystal structures and magnetic properties


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      Three new heterobimetallic cyanide-bridged complexes, {[Ni(L1)][Ag(CN)2]}[Ag(CN)2] ·2H2O (2), {[Mn(L1)][Ag(CN)2]} · 1.5H2O (3) and {[Mn(L3)(H2O)]2[Ag(CN)2]}ClO4 · 2H2O (4) (L1 =2,7,12-trimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene; L2 = N,N’-1,3-propylenebis(5-chlorosalicylideneiminate); L3 = N,N’-1,2-propylene-bis(5-bromosalicylideneiminate)), have been assembled using for the first time a new polyaza macrocycle nickel(II) compound [Ni(L1)](ClO4)2(1), or Schiff-base manganese(III) compounds and K[Ag(CN)2]. Single crystal X-ray diffraction analysis reveals that complexes 2 and 3 can be characterized as one-dimensional cationic and neutral single chain structure, respectively. Complex 3 forms a three-dimensional network via weak inter-chainAg…Aginteractions. Complex 4 belongs to a cyanide-bridged bimetallic sandwich-like cationic trinuclear structure containing Mn2Ag core with free ClO-4 as a counter anion, indicating that the Schiff-base ligand has an obvious influence on the structure of the cyanide-bridged complexes formed. Investigation of the magnetic susceptibilities of the cyanide-bridged Ag-Ni(II)/Mn(III) complexes showed the weak anti-ferromagnetic interaction between neighboring paramagnetic Ni(II) or Mn(III) ions bridged by the long NC-Ag-CN unit. From the best-fit of the magnetic susceptibility data of complexes 2 and 4 the magnetic coupling constant was determined to be J = −0.51 and −0.78 cm-1,respectively.

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