The novel metalloligand [Fe(bppd)3] (bppd=1,3-bis(4-pyridyl)-1, 3-propanedionate) for the crystal engineering of heterometallic coordination networks with different silver salts. Anionic control of the structures
The novel metalloligand [Fe(bppd)3] (bppd=1,3-bis(4-pyridyl)-1, 3-propanedionate) for the crystal engineering of heterometallic coordination networks with different silver salts. Anionic control of the structures
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DOI：
10.1039/c1ce05520h
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发表时间：
2011-01-01
期刊：
影响因子：
3.1
通讯作者：
Visconti, Marco
中科院分区：
文献类型：
--
作者：
Carlucci, Lucia;Ciani, Gianfranco;Visconti, Marco
本文报道了一种新型的三配位金属配体[Fe-III(Bppd)(3)](bppd，1，3-双(4-吡啶)-1，3-丙二酸酯)的异金属配位网络的晶体工程。构筑块[Fe(Bppd)3]与Delta和Lambda的平衡堆积形成扭曲的八面体手性结构，具有六个外取向的吡啶供体基团，适合通过与外部金属离子相互作用而联网。它与许多银盐AgX(X=BF4-、ClO4-、PF6-、AsF6-、SbF6-、NO3-、CF3SO3-、对甲苯磺酸盐)反应，得到结构取决于反阴离子X-的聚合物。对于拟球形阴离子(如BF4-、ClO4-、PF6-、AsF6-和SbF6-)，由于金属配体只使用六个吡啶供体中的四个来结合银离子，所以得到了具有SQL拓扑结构的二维聚合物物种[Fe(Bppd)(3)Ag](X)。与Ag(CF3SO3)的反应得到了完全不同类型的[Fe(Bppd)(3)Ag](+)2D聚合物骨架，金属配体也只使用了四个吡啶基团进行网络连接，即由两个重叠的蜂窝片组成的双层物种，呈现(4(3).6(3))拓扑结构。有趣的是，用AgNO_3得到了一个三维骨架[Fe-2(Bppd)(6)Ag-3](NO_3)(3)，它与以前的物种一样，通过两侧的银桥连接在一起，形成了一个5，4-连接的二重互穿网络。与对甲苯磺酸银反应生成了具有6个连接金属配体和3个和4个连接银离子的复杂的三维纳米孔网络[Fe-3(Bppd)(9)Ag-5](对甲苯磺酸盐)(5)。这个网络的一个有趣的合理化是，它由一维平行的六角形截面的纳米管图案组成，这些纳米管由Ag三桥原子横向互连，从而生成整个3D阵列。我们观察到，在这些物种中，金属配体使用数量可变的吡啶供体进行网络连接，即4个、5个和6个，导致框架的复杂性和维度增加，这些框架强烈依赖于阴离子形状和性质。类似的金属配体[Al-III(Bppd)(3)]与相同的AgX盐在相似的条件下反应生成多晶材料，在三氟化银和对甲苯磺酸盐的情况下，它们与相应的含铁物种同构，从它们的X射线粉末衍射谱中可以看出这一点。
The crystal engineering of heterometallic coordination networks based on the novel tris-chelate metalloligand [Fe-III(bppd)(3)] (bppd 1,3-bis(4-pyridyl)-1,3-propanedionate) is reported here. The building block [Fe(bppd) 3] crystallizes with a balanced packing of the Delta and Lambda forms and exhibits distorted octahedral chiral structure with six exo-oriented pyridyl donor groups suitable for networking via interactions with external metal ions. It was reacted with many silver salts AgX (X = BF4-, ClO4-, PF6-, AsF6-, SbF6-, NO3-, CF3SO3-, tosylate) giving polymeric products with structures depending on the nature of the counter-anions X-. With pseudo-spherical anions (such as BF4-, ClO4-, PF6-, AsF6- and SbF6-) 2D polymeric species [Fe(bppd)(3)Ag](X) are obtained showing sql topology, because the metalloligands use only four, out of the six pyridyl donors, to bind silver ions. The reaction with Ag (CF3SO3) affords a quite different type of [Fe(bppd)(3)Ag](+) 2D polymeric frame, with the metalloligands that again employ only four pyridyl groups for networking, i.e. a double layered species comprised of two superimposed honeycomb sheets, exhibiting a (4(3).6(3)) topology. By using AgNO3 a 3D framework, [Fe-2(bppd)(6)Ag-3](NO3)(3), is obtained that, interestingly, consists of double layers like those of the previous species connected via Ag bridges on both sides to produce a binodal 5,4-connected 2-fold interpenetrated network. The reaction with silver p-toluenesulfonate produces the complex 3D nanoporous network [Fe-3(bppd)(9)Ag-5](tosylate)(5) with 6-connected metalloligands and 3- and 4-connected silver ions. An interesting rationalization of this network is that it is comprised of 1D parallel nanotubular motifs of hexagonal section with square-meshed walls; these nanotubes are laterally interconnected by Ag triple-bridging atoms to generate the whole 3D array. We observe that in these species the metalloligands use a variable number of pyridyl donors for networking, i.e. four, five and six, leading to frames of increased complexity and dimensionality that are strongly dependent on the anionic shape and nature. The reactions of the analogous metalloligand [Al-III(bppd)(3)] with the same AgX salts under similar conditions produce polycrystalline materials that in the cases of silver triflate and tosylate are isostructural with the corresponding iron containing species, as evidenced by their X-ray powder diffraction spectra.