Two novel heteronuclear manganese-dysprosium complexes have been synthesized and characterized, both of which contain a [Mn_2Dy_2O_2] core ligated by eight But CO_2-anions and four neutral ligands. In complex 1, [Mn_2...Two novel heteronuclear manganese-dysprosium complexes have been synthesized and characterized, both of which contain a [Mn_2Dy_2O_2] core ligated by eight But CO_2-anions and four neutral ligands. In complex 1, [Mn_2Dy_2O_2(Bu^tCO_2)_8(Bu^tCO_2H)_4], all the four neutral ligands coordinated to Dy^(3+) are pivalic acids; Instead, two of these four pivalic acids have been replaced by ethanol in complex 2 [Mn2 Dy2 O2(Bu^tCO_2)_8(Bu^tCO_2H)_2(CH_3CH_2OH)_2]. The crystal of complex 1(C_(60)H_(112)Dy_2Mn_2O_(26), Mr = 1684.36) belongs to the orthorhombic system, space group Pbca with a =19.853(3), b = 18.565(3), c = 20.952(3) ?, V = 7723(2) ?3, Z = 4, Dc = 1.449 g/cm^3, S = 1.210, μ =2.302 mm^(-1), F(000) = 3448, the final R = 0.0802 and w R = 0.1570 for 8736 independent reflections.The crystal of complex 2(C_(54)H_(104)Dy_2Mn_2O_(24), Mr = 1572.25) belongs to the monoclinic system,space group C2/c with a = 27.814(6), b = 13.194(3), c = 22.912(5) ?, β = 124.89(3)o, V = 6897(3) ?3,Z = 4, Dc = 1.514 g/cm^3, S = 1.086, μ = 2.570 mm^(-1), F(000) = 3208, the final R = 0.0256 and wR =0.0592 for 7763 independent reflections. The cyclic voltammogram and catalytic activity measurements of complex 1 suggest that this type of complex can serve as a catalyst for oxygen-evolving reaction.展开更多
基金supported by the National Key Research and Development Program of China(No.2017YFA0503704)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB17030600)National Natural Science Foundation of China(No.31770258)
文摘Two novel heteronuclear manganese-dysprosium complexes have been synthesized and characterized, both of which contain a [Mn_2Dy_2O_2] core ligated by eight But CO_2-anions and four neutral ligands. In complex 1, [Mn_2Dy_2O_2(Bu^tCO_2)_8(Bu^tCO_2H)_4], all the four neutral ligands coordinated to Dy^(3+) are pivalic acids; Instead, two of these four pivalic acids have been replaced by ethanol in complex 2 [Mn2 Dy2 O2(Bu^tCO_2)_8(Bu^tCO_2H)_2(CH_3CH_2OH)_2]. The crystal of complex 1(C_(60)H_(112)Dy_2Mn_2O_(26), Mr = 1684.36) belongs to the orthorhombic system, space group Pbca with a =19.853(3), b = 18.565(3), c = 20.952(3) ?, V = 7723(2) ?3, Z = 4, Dc = 1.449 g/cm^3, S = 1.210, μ =2.302 mm^(-1), F(000) = 3448, the final R = 0.0802 and w R = 0.1570 for 8736 independent reflections.The crystal of complex 2(C_(54)H_(104)Dy_2Mn_2O_(24), Mr = 1572.25) belongs to the monoclinic system,space group C2/c with a = 27.814(6), b = 13.194(3), c = 22.912(5) ?, β = 124.89(3)o, V = 6897(3) ?3,Z = 4, Dc = 1.514 g/cm^3, S = 1.086, μ = 2.570 mm^(-1), F(000) = 3208, the final R = 0.0256 and wR =0.0592 for 7763 independent reflections. The cyclic voltammogram and catalytic activity measurements of complex 1 suggest that this type of complex can serve as a catalyst for oxygen-evolving reaction.