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首页> 外文期刊>Acta Crystallographica, Section B. Structural science, crystal engineering and materials >3-(Pyridin-4-yl)acetylacetone: a donor ligand towards mercury(II) halides and a versatile linker for complex materials
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3-(Pyridin-4-yl)acetylacetone: a donor ligand towards mercury(II) halides and a versatile linker for complex materials

机译：3-（吡啶-4-基）乙酰丙酮：氟汞（II）卤化物的供体配体和用于复合物质的通用连接物

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摘要

The ditopic organic molecule 3-(pyridin-4-yl)acetylacetone (HacacPy) acts as a pyridine-type ligand towards HgX_2 (X = Cl, Br, I). The nature of the anion and the ligand-to-cation ratio dominate the outcome of the reaction. Two different coordination compounds form with HgCl_2, namely a ligand-rich mononuclear complex, HgCl_2(HacacPy)_2, and a ligand-deficient one-dimensional chain polymer, [Hg(μ-Cl)_2(HacacPy)]_∞~1, with five-coordinated Hg~II cations. Two compounds are also observed for HgBr2, a molecular complex isomorphous to the chloride derivative and a chain polymer with the composition [Hg- (μ-Br)Br(HacacPy)]_∞~1, in which the cations are four-coordinated. The ligandrich mononuclear and ligand-deficient polymeric chloride and bromide complexes may be interconverted via thermal degradation and mechanochemical synthesis. In contrast to the chloride and bromide compounds, the reaction product with HgI_2 does not depend on the ligand-to-cation ratio but corresponds to [Hg(μ-I)I(HacacPy)]_∞~1, isomorphous to the bromide derivative. The N-coordinated HacacPy complexes could not be deprotonated and further crosslinked with a second cation. Synthesis of mixed-metal products could be achieved, however, by deprotonation of the acetylacetone moiety in HacacPy and formation of tris-chelated Fe(acacPy)_3 and Al(acacPy)_3 complexes in the first step. These mononuclear building blocks act as bridging poly(pyridine) ligands towards HgII halides and form two structure types. The first represents a one-dimensional ladder, with the tris(ligand) complexes acting as triconnected nodes and the HgII halides acting as linkers. In the alternative unprecedented product, both the tris(ligand) complexes and the [HgX_2(μ-X)HgX] groups act as equivalent triconnected nodes. They form a uninodal two-dimensional coordination network with vertex symbol 4.8~2 and fes topology.
机译：DITopic有机分子3-（吡啶-4-基）乙酰丙酮（HACACPY）用作朝向HGX_2的吡啶型配体（X = CL，BR，I）。阴离子的性质和配体至阳离子比导地位反应的结果。两种不同的配位化合物与HgCl_2，即富含配体的单核络合物，HgCl_2（Hacacpy）_2和配体缺陷的一维链聚合物，[Hg（μ-Cl）_2（Hacacpy）] _〜〜1，用五个协调的HG〜II阳离子。对于HGBR2，也观察到两种化合物，其与氯化物衍生物的分子复合物和具有组合物的链聚合物[Hg-（μ-Br）Br（Hacacpy）] _〜1，其中阳离子是四个协调的。 Ligandrich单核和配体缺陷的聚合物氯化物和溴化物复合物可以通过热降解和机械化学合成互连。与氯化物和溴化物化合物相比，具有Hgi_2的反应产物不依赖于配体与阳离子比例，但对应于[Hg（μ-I）I（HacaCpy）] _〜1，对溴化物衍生物同表示。 N-协调的Hacacpy复合物不能脱抗栓塞并进一步与第二个阳离子交联。然而，通过在第一步中通过在HacaCaCy中的乙酰丙酮部分的去邻和形成Tris-Chelated Fe（acaCpy）_3和Al（acaCpy）_3络合物中的乙酰丙酮部分的去质子来实现混合金属产物的合成。这些单核构建块充当朝向HGII卤化物的桥接聚（吡啶）配体，形成两种结构类型。首先代表一维梯形，其具有作为三角形节点的Tris（配体）复合物，以及用作接头的HGII卤化物。在替代的前所未有的产品中，TRIS（配体）复合物和[HGX_2（μ-X）HGX]组充当等效的三角形节点。它们形成一个多透明的二维协调网络，顶点符号4.8〜2和FES拓扑。

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