Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

摘要

Various metalloligands and inorganic-organic hybrid bridging ligands have been incorporated in polynuclear complexes and bimetallic coordination polymers. Ferrocene, exhibiting redox activity and facile chemical modification, is a versatile metalloligand component. However, most metal complexes with ferrocene-containing ligands form discrete low-dimensional chelate complexes or coordination polymers. Thus, we designed and synthesized ferrocene-based multidentate ligands, 1,2-di(4-pyridylthio)ferrocene (L1) and 1,2-di(2-pyridylthio)ferrocene (L2). Here we report the synthesis and structures of molecular square complexes and coordination polymers containing L1, which reacted with M(hfac)(2) (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) and AgCF3SO3 to yield molecular square complexes [M(hfac)(2)(L1)](2)center dot 2C(6)H(5)CH(3)[M = Ni (1) and Co (2)] and [Ag(CF3SO3)(L1)(H2O)(0.5)](2)center dot 2CH(2)Cl(2)center dot H2O (3). The molecular square units comprise two metal ions bridged by two ligands. Isomorphic complexes 1 and 2 accommodate two toluene molecules above and below the molecular square. Ll reacted with Cu(hfac)(2) and CuI to yield zigzag, {[Cu(hfac)(2) (LI)]}(n)center dot 0.25n(CH2Cl2) (4), and ribbon-shaped, {[Cu4I4(L1)(2)]}(n) (5), coordination polymers. In 4, L1 behaves as a bidentate N,N-ligand bridging the Cu-II ions, while in 5 it acts as a tridentate S,N,N-ligand linking the stepped-cubane Cu4I4 units. L1 reacted with AgX to form two-dimensional coordination polymers {[Ag(ClO4)(L1)]}(n) (6) and {[Ag(L1)]PF6}(n) (7), in which it acted as a tetradentate S,S,N,N-ligand. These complexes have topologies based on multidentate coordination of 1,2-substituted L1.