Studies on Heterodinuclear Metal Complexes

(1)2，6-二甲酰基-4-甲基苯酚与H_2N-(CH_2)_m-NH_2(m=2，3)和H_2N-(CH_2)_n-NH_2(n=3，4)经2：1：1缩合而成的苯酚基双核大环，形成了异双核的Ni(II)Mn(II)、Cu(II)Mn(II)、Ni(II)Co(II)、Cu(II)Co(II)和Cu(II)Ni(II)配合物。低温磁学研究表明，除Ni(II)、Mn(II)和Ni(II)、Co(II)外，其余配合物均存在反铁磁相互作用。所有的配合物在溶液中都是稳定的，并形成了不寻常的氧化态配合物，如Ni(I)Co(II)、Ni(I)Co(I)等。在液氮温度下，铜(II)-Ni(II)配合物表现出很强的反铁磁性相互作用，以自旋对基态存在。对S_T=1/2态的ESR研究表明，CuNi核上存在自旋离域。(2)合成了一个相关大环的Co(II)Pb2+配合物，该配合物具有两个不同的N_2O_2和N_2O_3施主配位，共用两个酚氧。(3)合成了两个不同的N(胺)_2O_2和N(亚胺)_2O_2金属结合位共用两个酚氧基的酚基双核大环，并合成了一系列铜(II)M(II)(M=Mn，Co，Ni，Cu，Zn)配合物。络合物的循环伏安曲线在电极上表现出相当大的稳定性，并形成了铜(I)、锰(II)等罕见的氧化态化合物。

(1) Phenol-based dinucleating macrocycles, derived from the 2 : 1 : 1 condensation of 2,6-diformyl-4-methylphenol, H_2N-(CH_2)_m-NH_2(m=2,3) and H_2N-(CH_2)_n-NH_2(n=3,4), formed heterodinuclear Ni(II)Mn(II), Cu(II)Mn(II), Ni(II)Co(II), Cu(II)Co(II) and Cu(II)Ni(II) complexes whose molecular structures were determined by X-ray chrystallography and physicochemical properties were examined. Cryomagnetic studies revealed antiferromagnetic interaction in the complexes except for Ni(II)Mn(II) and Ni(II)Co(II). All the complexes were stable in solution and form unusual oxidation-state complexes such as Ni(I)Co(II), Ni(I)Co(I), etc. The Cu(II)Ni(II) complex showed a very strong antiferromagnetic interaction to exist as the spin-doublet ground state at liquid nitrogen temperature. ESR study for the S_T=1/2 state showed a spin-delocalization over the CuNi core.(2) A Co(II)Pb(II) complex of a related macrocycle, having two dissimilar metal-binding sites of the N_2O_2 and N_2O_3 donor sets sharing two phenolic oxygens, was prepared. It acts as a reversible dioxygen-carrier in solid state owing to a neighboring effect of the Pb(II) ion.(3) Phenol-based dinucleating macrocycles, with two dissimilar N(amine)_2O_2 and N(imine)_2O_2 metal-binding sites sharing two phenolic oxygens, were prepared and a series of Cu(II)M(II)(M=Mn, Co, Ni, Cu, Zn) complexes were derived. CV for the complexes showed a considerable stabilization on electrode and formation of unusual oxidation-state compounds like Cu(I)Mn(II) etc.