摘要
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all the four neutral ligands coordinated to Dy^(3+) are pivalic acids; Instead, two of these four pivalic acids have been replaced by ethanol in complex 2 [Mn2 Dy2 O2(Bu^tCO_2)_8(Bu^tCO_2H)_2(CH_3CH_2OH)_2].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.
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all the four neutral ligands coordinated to Dy^(3+) are pivalic acids; Instead, two of these four pivalic acids have been replaced by ethanol in complex 2 [Mn2 Dy2 O2(Bu^tCO_2)_8(Bu^tCO_2H)_2(CH_3CH_2OH)_2].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.
作者
赵国清
李彦洗
陈长辉
张纯喜
ZHAO Guo-Qing;LI Yan-Xi;CHEN Chang-Hui;ZHANG Chun-Xi
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)