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Structural versatility of alkali metal coordination polymers driven by arylhydrazones of β-diketones

机译:β-二酮芳基hydr酮驱动的碱金属配位聚合物的结构通用性

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摘要

The self-assembly reaction of arylhydrazones of β-diketones (AHBD), namely 2-[2-(2,4-dioxopentan-3-ylidene)hydrazinyl]benzenesulfonic acid (H_2L~1) and 2-[2-(4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl]benzenesulfonic acid (H_2L~2), with sodium or potassium hydroxides in MeOH/H_2O (1/1, v/v) produces a series of coordination compounds, [Na_3(μ_3-HL~1)_ 2(μ_4-HL~1)(μ-H_2O)(H_ 2O)_2]_n (1), [Na_2(HL~ 1)_2(μ-H_2O)_2(H_2O)_ 4]·4H_2O (2), [Na(HL~2)(μ-H_ 2O)(H_2O)_2]_n·nH_2O (3), [K(μ_4-HL~1)(μ_3-H_2O)]_ n (4), and [K(μ_4-HL~2)(H_2O)]_ n (5), which include the one-dimensional (3), two-dimensional (2D) (1, 4), and three-dimensional (3D) (5) coordination polymers, as well as the zero-dimensional dimer (2). Compounds 1-5 were isolated as air stable crystalline solids and characterized by IR, ~1H, and ~(13)C{~1H} NMR spectroscopy, elemental, differential thermal, and single-crystal X-ray diffraction analysis. The latter shows that the monodeprotonated HL~(1-) (L = L~1, L~2) anions act as multiple O-donors through the sulfonate and carbonyl groups and are also capable of simultaneously bridging three and/or four metal cations (in 1, 4, and 5), thus giving rise to the intricate 2D and 3D coordination networks. Their topological analysis reveals the trinodal 3,4,7-connected (in 4) and pentanodal 3,4-connected (in 1) underlying 2D nets with novel types of topologies, as well as the uninodal 4-connected 3D framework with the sra (SrAl_2) topology (in 5).
机译:β-二酮(AHBD)的芳基hydr(2- [2-(2,4-二氧戊丹-3-亚烷基)肼基]苯磺酸(H_2L〜1)与2- [2-(4, 4-二甲基-2,6-二氧杂环己基)肼基]苯磺酸(H_2L〜2)与氢氧化钠或氢氧化钾在MeOH / H_2O(1/1,v / v)中生成一系列配位化合物[Na_3(μ_3- HL〜1)_ 2(μ_4-HL〜1)(μ-H_2O)(H_2O)_2] _n(1),[Na_2(HL〜1)_2(μ-H_2O)_2(H_2O)_ 4]· 4H_2O(2),[Na(HL〜2)(μ-H_2O)(H_2O)_2] _n·nH_2O(3),[K(μ_4-HL〜1)(μ_3-H_2O)] _ n(4) ,以及[K(μ_4-HL〜2)(H_2O)] _ n(5),包括一维(3),二维(2D)(1、4)和三维(3D) (5)配位聚合物,以及零维二聚体(2)。分离出化合物1-5,为空气稳定的结晶固体,并通过IR,〜1H和〜(13)C {〜1H} NMR光谱,元素,差热和单晶X射线衍射分析进行表征。后者表明,单去质子化的HL〜(1-)(L = L〜1,L〜2)阴离子通过磺酸根和羰基充当多个O供体,并且还能够同时桥接三个和/或四个金属阳离子(1、4和5中),因此产生了复杂的2D和3D协调网络。他们的拓扑分析揭示了具有新型拓扑类型的底层3D网络的三节点3,4,7连接(共4个)和五节点3,4连接(合1)以及具有sra的单节点4连接3D框架(SrAl_2)拓扑(在5中)。

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