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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all the four neutral ligands coordinated to Dy3+ are pivalic acids; Instead, two of these four pivalic acids have been replaced by ethanol in complex 2 [Mn2Dy2O2(ButCO2)8(ButCO2H)2(CH3CH2OH)2].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)
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