Multiparameter High-Throughput and in Situ X-ray Diffraction Study of Six New Bismuth Sulfonatocarboxylates: Discovery, Phase Transformation, and Reaction Trends
Multiparameter High-Throughput and in Situ X-ray Diffraction Study of Six New Bismuth Sulfonatocarboxylates: Discovery, Phase Transformation, and Reaction Trends
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DOI：
10.1021/acs.inorgchem.8b01563
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发表时间：
2018-08-20
影响因子：
4.6
通讯作者：
Stock, Norbert
中科院分区：
文献类型：
--
作者：
Albat, Martin;Stock, Norbert
采用高通量方法，在水热反应条件下系统地研究了Bi3+/4,8-二磺酰I-2,6-萘二甲酸(H4DSNDC)/H2O/添加剂(HNO3或NaOH)体系。在 500 多个反应中研究了起始原料的摩尔比、pH 值以及反应温度和时间的影响。产物的形成对合成参数的微小变化高度敏感，但从反应物的澄清溶液开始可重复地获得六种新的磺基羧酸铋。所有化合物均根据单晶 X 射线衍射数据进行结构表征。完全去质子化的连接离子存在于 [Bi6O6(OH)(2)(H2O)(4)(DSNDC)] (1)、[Bi-2(OH)(2)(DSNDC)] (2)、[Bi8O7 (OH)(2) (H2O)(2) (DSNDC)(2) (3) 和[Bi7O5(OH)(3)(H2O)4(DSNDC)(2)]中心点 4H(2)O (4)，而大量酸的存在或较短的反应时间会导致生成具有非配位 -COOH 基团的化合物，[Bi-2(OH)(2)(H2O)(2)(DSNDC)(H2DSNDC)] (5) 和分别为{Bi6O4(OH)(4)(H2O)(12)(H2DSNDC)(3)]中心点xH(2)O(6)。所有六种结构中的无机建筑单元（IBU）彼此显着不同；文献中已经报道了在 2 ({Bi-2(OH)(2)})、5 (BiO8 多面体)和 6 ({Bi6O4(OH)(4)} 簇)中发现的 IBU，而在 1 (组成链 {Bi3O3(OH)}(无穷大))、3 ({Bi16O14(OH)(4)}簇)和 4 中观察到了新的 IBU （{Bi7O5(OH)(3)}簇）。反应温度和时间的系统变化表明它们对产物形成的明显影响。因此，在德国汉堡的 Deutsches Elektronen-Synchrotron 采用同步加速器辐射进行了原位粉末 X 射线衍射测量。在所有研究的原位反应中，首先观察到化合物 6，然后根据反应时间、温度以及起始材料的浓度转化为 1、2、4 和 5。
With the employment of high-throughput methods, the system Bi3+/4,8-disulfonyI-2,6-naphthalenedicarboxylic acid (H4DSNDC)/H2O/additive (HNO3 or NaOH) was systematically investigated under hydrothermal reaction conditions. The influence of the molar ratio of the starting materials, pH, and reaction temperature and time was investigated in more than 500 reactions. The product formation is highly sensitive toward small changes of the synthesis parameters, but six new bismuth sulfonatocarboxylates were reproducibly obtained starting from clear solutions of the reactants. All compounds were structurally characterized from single-crystal X-ray diffraction data. Fully deprotonated linker ions are found in [Bi6O6(OH)(2)(H2O)(4)(DSNDC)] (1), [Bi-2(OH)(2)(DSNDC)] (2), [Bi8O7 (OH)(2) (H2O)(2) (DSNDC)(2) (3), and [Bi7O5(OH)(3)(H2O)4(DSNDC)(2)]center dot 4H(2)O (4), while the presence of larger amounts of acid or short reaction times leads to compounds with noncoordinating -COOH groups, [Bi-2(OH)(2)(H2O)(2)(DSNDC)(H2DSNDC)] (5) and {Bi6O4(OH)(4)(H2O)(12)(H2DSNDC)(3)]center dot xH(2)O (6), respectively. The inorganic building units (IBUs) in all six structures differ substantially from each other; the IBUs found in 2 ({Bi-2(OH)(2)}), 5 (BiO8 polyhedron), and 6 ({Bi6O4(OH)(4)} cluster) have been reported in the literature, while new IBUs are observed for 1 (chains of composition {Bi3O3(OH)}(infinity)), 3 ({Bi16O14(OH)(4)} cluster), and 4 ({Bi7O5(OH)(3)} cluster). Systematic variation of the reaction temperature and time indicated their distinct influence on product formation. Hence, in situ powder X-ray diffraction measurements at Deutsches Elektronen-Synchrotron, Hamburg, Germany, employing synchrotron radiation were carried out. In all studied in situ reactions, compound 6 is first observed and subsequently transformed to 1, 2, 4, and 5, depending on the reaction time and temperature as well as concentration of the starting materials.