From Sequential to One-Pot Synthesis of Dipyrrin Based Grid-Type Mixed Metal鈥揙rganic Frameworks

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• 作者：Antoine B茅ziau ; St茅phane A. Baudron ; Audrey Fluck ; Mir Wais Hosseini
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：December 16, 2013
• 年：2013
• 卷：52
• 期：24
• 页码：14439-14448
• 全文大小：549K
• 年卷期：v.52,no.24(December 16, 2013)
• ISSN：1520-510X

文摘

Both sequential and one-pot strategies for the preparation of a series of grid-type mixed metal鈥搊rganic frameworks (MM鈥睲OFs) based on dipyrrin ligands appended with either a pyridyl or a phenyl-imidazolyl moiety have been investigated. For the stepwise approach, the differentiation between the two coordination sites (nature, charge, and denticity) was exploited for the synthesis of a family of five discrete Zn(II), Cu(II), and Pd(II) complexes. Acting as metallatectons, these construction building blocks lead to the formation of a series of MM鈥睲OFs upon self-assembly with CdCl₂. In these rhombic grid-type architectures, four consecutive metallatectons are bridged by Cd(II) cations adopting an octahedral coordination geometry with the chloride anions occupying apical positions, thus behaving as square nodes. The shape of the rhombus grids as well as the way they are packed (stacking or interpenetration) in the crystalline phase are controlled by the nature of metallatectons and the solvent molecules present in the crystals. Consequently, the heterometallic assemblies display different accessible voids, although they are built on layers with the same connectivity. More interestingly, as demonstrated by X-ray diffraction on both single crystals and microcrystalline powders, the same MM鈥睲OFs were obtained by a one-pot strategy through direct combinations of dipyrrin derivatives with the corresponding metal salts. This one-pot approach is efficient and more convenient than the sequential alternative, since the isolation, purification, and characterization of the, sometimes insoluble, metallatectons are not required.