Binding Features of {M(3d)(cbdc)2} Blocks (M(3d)=V~(IV)O,Cu~(II);cbdc~(2-)=Dianion of Cyclobutane-1,1-Dicarboxylic Acid) in Formation of Heterometallic Structures with d-Metal Cations

摘要

Compounds containing bis-chelate dianionic blocks {M(3d) (cbdc)2}~(2-) (M(3d)=V~(IV)O,Cu~(II)) with cations VO~(2+) and Cu~(2+) chelated by two anions of dicarboxylic acid have been prepared as crystals when aqueous solutions of vanadyl sulfate VOSO4·3H2O or copper sulfate CuSO4·5H2O have been allowed to react with sulfates of d-metals (Mn~(II),Co~(II),Ni~(II),Zn~(II),and Cd~(II)) and barium salt of cyclobutane-1,1-dicarboxylic acid (H2cbdc= C4H6(CO2H)2) in the 1:1:2 ratio.The nature of the M(3d) metal center has been found to influence on the structure of the heterometallic compounds formed.1D polymers [M(VO) (cbdc)2(EtOH)2(H2O)3]n (M=Mn (1),Co (2),Ni (3)),molecular dinuclear complex [Zn(VO)(cbdc)2(H2O)5]·H2O (4),and 1D polymer {[Cd(VO)(cbdc)2(H2O)5]·H2O}n (5) are formed when M(3d)= VIVO,whereas in the case of the bis-chelate block with the Cu~(II) atom,ionic compounds [M(H2O)6][Cu(cbdc)2(H2O)] (M=Mn (6),Co (7),Ni (8),Zn (9)) and 2D polymer {[CdCu(cbdc)2(H2O)2] ·2H2O}n have been synthesized.The isolation of paramagnetic centers in compounds 1–10 is confirmed by magnetic measurements and EPR spectroscopy.