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通过[HN(n-C4H9)3]3[WV(CN)8]·4H2O,4,4’-bipyridinedioxide(4,4’-dpdo)和MnCl2·4H2O或CuCl2·2H2O的反应得到两个新的基于八氰金属酸盐的三维异金属化合物,{[Mn2(4,4’-dpdo)(H2O)4][WIV(CN)8]}·6H2O(1)和{[Cu2(4,4’-dpdo)(H2O)][W(CN)8]}·CH3OH·H2O(2).其中,化合物1属正交晶系,空间群为P21212,晶胞参数为:a=10.397(2)-,b=11.321(2)-,c=12.295(3)-,Z=2;化合物2则属于单斜晶系,空间群为P21/c,晶胞参数为:a=13.038(3)-,b=13.784(3)-,c=13.225(3)-,β=93.44(3)°,Z=4.在化合物1中,每个[WIV(CN)8]4-单元呈反四棱柱几何构型,并通过桥连CN-离子与四个Mn2双核单元相连而形成波浪状的-W-Mn2-W-Mn2-交替层;层层之间又进一步通过与Mn离子配位的4,4′-dpdo配体桥连形成一个三维开放骨架结构.在化合物2中,每个[WIV(CN)8]4-离子依旧采取反四棱柱几何构型,它通过七个CN-离子分别与七个铜离子键连形成笼状波浪形的层;层层再进一步通过4,4′-dpdo配体桥连形成一个三维网络结构.由于4,4′-dpdo配体的较长刚性桥连作用,使得化合物1-2的开放骨架结构中形成许多被H2O或甲醇溶剂分子占据的空穴.值得一提的是,化合物1中,4,4′-dpdo配体表现出一种μ-4,4,4′,4′配位模式;据我们所知,这种配位模式虽然以前曾被理论预测过,但却是第一次被实验证实.磁性研究表明:化合物1表现出MnII离子之间的反铁磁耦合作用,而化合物2则体现了CuII离子之间的弱铁磁耦合相互作用.
The reaction of two new [HN (n-C4H9) 3] 3 [WV (CN) 8] · 4H2O, 4,4’-bipyridinedioxide (4,4’-dpdo) and MnCl2 · 4H2O or CuCl2 · 2H2O ([Mn2 (4,4’-dpdo) (H2O) 4] [WIV (CN) 8]} 6H2O (1) and {[Cu2 (4,4 ’ Compound 1 belongs to the orthorhombic system with space group P21212 and unit cell parameters are as follows: a = 10.397 (2) - dpdo (H2O)] [W (CN) 8] (2) -, c = 12.295 (3) -, Z = 2; Compound 2 belongs to the monoclinic system with space group P21 / c and unit cell parameters are as follows: a = 13.038 b = 13.784 (3) -, c = 13.225 (3) -, β = 93.44 (3) °, Z = 4. In compound 1 each of the [WIV (CN) 8] W-Mn2-W-Mn2-alternated layer was formed by bridging the CN- ions with four Mn2 binuclear units. The layers were further intercalated with Mn ions ’-dpdo ligand bridge to form a three-dimensional open framework.In compound 2, each [WIV (CN) 8] 4-ion still takes the anti-quadrangular prism geometry, which is separated by seven CN- A copper ion bond to form a cage-like wavy layer; layer and then further through the 4,4’-dpdo ligand bridge to form a Dimensional network structure. Due to the longer rigid bridging effect of 4,4’-dpdo ligands, a large number of holes occupied by H2O or methanol solvent molecules are formed in the open framework of compound 1-2. It is worth mentioning that, In compound 1, the 4,4’-dpdo ligand showed a μ-4,4,4 ’, 4’ coordination pattern; to the best of our knowledge, this coordination pattern, although previously theoretically predicted, It was the first time that it was confirmed by experiment.The magnetic study showed that compound 1 showed the antiferromagnetic coupling between MnII ions and that of compound 2 showed the weak iron-magnetic coupling interaction between CuII ions.