Dipyridyl β-diketonate complexes and their use as metalloligands in the formation of mixed-metal coordination networks
Dipyridyl β-diketonate complexes and their use as metalloligands in the formation of mixed-metal coordination networks
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DOI：
10.1039/c2dt12115h
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发表时间：
2012-01-01
影响因子：
4
通讯作者：
Warren, John E.
中科院分区：
文献类型：
--
作者：
Burrows, Andrew D.;Mahon, Mary F.;Warren, John E.
制备了铁（III）和铝（III）配合物1,3-二（4-吡啶基）丙烷-1,3-dionato （dppd）和1,3-二（3-吡啶基）丙烷-1,3-dionato （dmppd）、[Fe(dppd)(3)] 1、[Fe(dmppd)(3)] 2、[Al(dppd)(3)] 3和[Al(dmppd)(3)] 4。这些配合物采用金属中心含有扭曲的八面体几何形状的分子结构。相反，铜（II）和锌（II）配合物[Cu(dppd)(2)] 5和[Zn(dmppd)(2)] 6都形成聚合物结构，其中吡啶基配位到邻近金属中心的轴向位置，将离散的方形平面配合物连接成二维网络。铕配合物[Eu(dmppd)(2)(H2O)(4)]Cl中心点2EtOH中心点0.5H(2) o7形成含有离散阳离子的结构，通过氢键连接成片，而镧配合物[La(dmppd)(3)(H2O)]中心点2H(2) o8采用一维网络结构，通过氢键连接成片。铁配合物1和2在与银(I)盐的反应中充当金属配体，其产物的性质取决于存在的反离子。因此，1与AgBF4反应得到[AgFe(dppd)(3)]BF4中心点dmso9，其中银中心将金属配体连接成离散的纳米管，而与AgPF6和AgSbF6反应得到[AgFe(dppd)(3)]PF6中心点3.28 dmso10和[AgFe(dppd)(3)]SbF6中心点1.25 dmso11，其中金属配体连接成片状。在这三种情况下，金属配体上的六个吡啶基中只有四个是配位的。2与AgNO3反应得到[Ag2Fe(dmppd)(3)(ONO2)]NO3中心点MeCN中心点ch2cl12。化合物12采用层状结构，其中所有的吡啶基都配位到银中心，另外，在两个银中心之间有一个硝酸盐离子桥接。[Ag2Fe(dmppd)(3)(O2CCF3)] CF3CO2中心点2MeCN中心点0.25CH(2)Cl(2) 13采用了类似的结构，其中桥接的三氟乙酸离子与12中的硝酸盐离子起相同的作用。
The iron(III) and aluminium(III) complexes of 1,3-di(4-pyridyl)propane-1,3-dionato (dppd) and 1,3-di(3-pyridyl)propane-1,3-dionato (dmppd), [Fe(dppd)(3)] 1, [Fe(dmppd)(3)] 2, [Al(dppd)(3)] 3 and [Al(dmppd)(3)] 4 have been prepared. These complexes adopt molecular structures in which the metal centres contain distorted octahedral geometries. In contrast, the copper(II) and zinc(II) complexes [Cu(dppd)(2)] 5 and [Zn(dmppd)(2)] 6 both form polymeric structures in which coordination of the pyridyl groups into the axial positions of neighbouring metal centres links discrete square-planar complexes into two-dimensional networks. The europium complex [Eu(dmppd)(2)(H2O)(4)]Cl center dot 2EtOH center dot 0.5H(2)O 7 forms a structure containing discrete cations that are linked into sheets through hydrogen bonds, whereas the lanthanum complex [La(dmppd)(3)(H2O)]center dot 2H(2)O 8 adopts a one-dimensional network structure, connected into sheets by hydrogen bonds. The iron complexes 1 and 2 act as metalloligands in reactions with silver(I) salts, with the nature of the product depending on the counter-ions present. Thus, the reaction between 1 and AgBF4 gave [AgFe(dppd)(3)]BF4 center dot DMSO 9, in which the silver centres link the metalloligands into discrete nanotubes, whereas reactions with AgPF6 and AgSbF6 gave [AgFe(dppd)(3)]PF6 center dot 3.28DMSO 10 and [AgFe(dppd)(3)]SbF6 center dot 1.25DMSO 11, in which the metalloligands are linked into sheets. In all three cases, only four of the six pyridyl groups present on the metalloligands are coordinated. The reaction between 2 and AgNO3 gave [Ag2Fe(dmppd)(3)(ONO2)]NO3 center dot MeCN center dot CH2Cl2 12. Compound 12 adopts a layer structure in which all pyridyl groups are coordinated to silver centres and, in addition, a nitrate ion bridges between two silver centres. A similar structure is adopted by [Ag2Fe(dmppd)(3)(O2CCF3)] CF3CO2 center dot 2MeCN center dot 0.25CH(2)Cl(2) 13, with a bridging trifluoroacetate ion playing the same role as the nitrate ion in 12.