Structural Diversity of Bismuth(III) Thiophenemonocarboxylates Isolated from Aqueous Solutions
Structural Diversity of Bismuth(III) Thiophenemonocarboxylates Isolated from Aqueous Solutions
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DOI：
10.1002/ejic.201601368
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发表时间：
2017-03-17
影响因子：
2.3
通讯作者：
Knope, Karah E.
中科院分区：
文献类型：
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作者：
Adcock, Alyssa K.;Batrice, Rami J.;Knope, Karah E.
以铋前驱体与2-噻吩羧酸（HTMC）和吡啶在水中进行室温反应，合成了5个新型含吡啶阳离子的双- iii -噻吩单羧酸酯（Bi-III-TMC）化合物。用单晶x射线衍射对其结构进行了表征，并用拉曼光谱和热重分析对其中两个化合物进行了进一步表征。这些化合物的固态结构是由阴离子BiIII构建单元构成的，这些单元在核、整体连通性和维度上都有所不同。当以较低的金属/配体比使用硝酸铋时，形成Hpy[Bi(TMC) 4(HTMC)] (1), Hpy[Bi(TMC) 4(HTMC)](1)由第二配位球吡啶阳离子电荷平衡的单核单元组成。随着金属/配体比例的增加，以及硝酸盐浓度的增加，Hpy[Bi-2(TMC)(6)(NO3)](2)中[Bi-2(TMC)(3)(NO3)](3)中[Bi-2(TMC)(3)(2)] -二聚体的硝酸盐和羧酸桥链以及Hpy[Bi(TMC)(3)(NO3)](3)中[Bi-2(TMC)(3)]-二聚体的硝酸盐桥接链被分离出来。从Bi2O3开始，形成多晶体（Hpy）(2)[Bi-2(TMC)(8)](4)和（Hpy）(2)[Bi-2(TMC)(8)](5)，两者都含有由羧酸基团桥接的铋中心，形成由吡啶阳离子电荷平衡的二聚体单元。本文讨论了其中15种化合物的合成条件，以及它们的固态结构化学。本文还报道了1和3的热稳定性以及化合物的光谱表征。
Five novel Bi-III-thiophenemonocarboxylate (Bi-III-TMC) compounds containing pyridinium cations have been synthesized from room-temperature reactions of bismuth precursors with 2-thiophenecarboxylic acid (HTMC) and pyridine in water. The structures have been determined by single-crystal Xray diffraction, and two of the compounds have been further characterized by Raman spectroscopy and thermogravimetric analysis. The solid-state structures of the compounds are built from anionic BiIII building units that vary in nuclearity, overall connectivity, and dimensionality. When using bismuth nitrate at a relatively low metal/ligand ratio, Hpy[Bi(TMC) 4(HTMC)] (1) is formed, which consists of mononuclear units charge-balanced by second coordination sphere pyridinium cations. With increasing metal/ligand ratios, and by consequence, increasing nitrate concentration, nitrate and carboxylate-bridged chains of [Bi-2(TMC)(3)(NO3)]-units in Hpy[Bi-2(TMC)(6)(NO3)] (2), and nitratebridged [Bi-2(TMC)(3)(NO3)(2)] 2-dimers in Hpy[Bi(TMC)(3)(NO3)] (3) are isolated. Starting from Bi2O3, polymorphs (Hpy)(2)[Bi-2(TMC)(8)] (4) and (Hpy)(2)[Bi-2(TMC)(8)] (5) are formed, both of which contain bismuth centers bridged by carboxylate groups to form dimeric units that are charge-balanced by pyridinium cations. Presented herein is a discussion of the synthetic conditions over which 15 were isolated, and their solid-state structural chemistry. The thermal stability of 1 and 3, and the spectroscopic characterization of the compounds, are also reported.