两种新型的锰镝异核金属化合物被合成并表征出来，它们都含有[Mn2Dy2O2]骨架，八个特戊酸根和四个中性配体。在化合物1[Mn2Dy2O2(ButCO2)8(ButCO2H)4]中，四个中性特戊酸配体均配位在Dy3+上；在化合物2[Mn2Dy2O2(ButCO2)8(ButCO2H)2(CH3CH2OH)2]中，四个特戊酸配体中的两个被乙醇分子替代。单晶结构解析表明：化合物1（C30H56DyMnO13，Mr= 842.18）属于正交晶系，空间群为Pbca，晶胞参数为a= 19.853(3)，b= 18.565(3)，c= 20.952(3) Å，V= 7723(2) Å3，Z= 8，Dc= 1.449 g/cm3，S= 1.210，μ= 2.302 mm-1，F(000)= 3448，R =0.0802，wR =0.1570，其中有8736个独立衍射点；化合物2（C54H104Dy2Mn2O24,Mr = 1572.25）属于单斜晶系，空间群为C2/c，晶胞参数为a= 27.814(6)，b= 13.194(3)，c= 22.912(5) Å，β= 124.89(3)º，V= 6897(3) Å3，Z= 4，Dc= 1.514 g/cm3，S= 1.086，μ= 2.570 mm-1，F(000)= 3208，R =0.0256，wR =0.0592，其中有7763个独立衍射点。化合物1的循环伏安和放氧测试表明这类化合物可以作为放氧反应的催化剂。

Two novel heteronuclear manganese-dysprosium complexes have been synthesized and characterized, both of which contain a [Mn2Dy2O2] core ligated by eight ButCO2- anions and four neutral ligands. In complex 1, [Mn2Dy2O2(ButCO2)8(ButCO2H)4], all the four neutral ligands coordinated to Dy3+ are pivalic acids; Instead, two of these four pivalic acids have been replaced by ethanol in complex 2 [Mn2Dy2O2(ButCO2)8(ButCO2H)2(CH3CH2OH)2]. The crystal of complex 1 (C60H112Dy2Mn2O26, Mr = 1684.36) belongs to the orthorhombic system, space group Pbca with a = 19.853(3), b = 18.565(3), c = 20.952(3) Å, V = 7723(2) Å3, Z = 4, Dc = 1.449 g/cm3, S = 1.210, μ = 2.302 mm-1, F(000) = 3448, the final R = 0.0802 and wR = 0.1570 for 8736 independent reflections. The crystal of complex 2 (C54H104Dy2Mn2O24, 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) Å, β = 124.89(3)º, V = 6897(3) Å3, Z = 4, Dc = 1.514 g/cm3, 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 measure- ments of complex 1 suggest that this type of complex can serve as a catalyst for oxygen-evolving reaction.

Syntheses, Crystal Structures and Catalytic

Activities of Two Novel Mn2Dy2O2 Complexes

ZHAO Guo-Qing(赵国清)  LI Yan-Xi(李彦洗)

 CHEN Chang-Hui(陈长辉)  ZHANG Chun-Xi(张纯喜)

Chinese J. Struct. Chem., 38, 109(2019)