Hexagonal Microparticles from Hierarchical Self-Organization of Chiral Trigonal Pd3L6 Macrotetracycles
Hexagonal Microparticles from Hierarchical Self-Organization of Chiral Trigonal Pd3L6 Macrotetracycles
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DOI：
10.1016/j.xcrp.2020.100303
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发表时间：
2021-01
影响因子：
8.9
通讯作者：
Ondřej Jurček;Nonappa;Elina Kalenius;Pia Jurček;J. Linnanto;R. Puttreddy;Hennie Valkenier;N. Houbenov;M. Babiak;M. Peterek;A. Davis;R. Marek;K. Rissanen
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作者：
Ondřej Jurček;Nonappa;Elina Kalenius;Pia Jurček;J. Linnanto;R. Puttreddy;Hennie Valkenier;N. Houbenov;M. Babiak;M. Peterek;A. Davis;R. Marek;K. Rissanen
利用固有的手性、不对称或多异位配体构建结构复杂的结构是金属超分子化学的主要挑战。此外，这种复合体的层次自组织是独一无二的。在这里，我们介绍了一种水溶性的、面亲性的、两性的、手性的、不对称的、杂三位的配体，它是从天然胆酸熊去氧胆酸中衍生出来的。我们发现，通过超分子转金属反应，使用硝酸盐Cu（II）或Fe(III)，随后使用Pd(II)，可以得到超手性pd3l6配合物。尽管pd3l6可以形成几种可能的构象异构体，但由于配体的不对称性和附着在类固醇支架上的氨基甲酸酯-吡啶基部分的相对灵活性，只能得到具有c3旋转对称性的单一产物。最后，我们证明了这些两亲性配合物可以在水介质中自组织成六边形微粒。这一发现可能导致由天然、丰富且相对便宜的甾体化合物制成的新型自组装金属有机功能材料的发展。
Construction of structurally complex architectures using inherently chiral, asymmetric, or multi-heterotopic ligands is a major challenge in metallosupramolecular chemistry. Moreover, the hierarchical self-organization of such complexes is unique. Here, we introduce a water-soluble, facially amphiphilic, amphoteric, chiral, asymmetric, and hetero-tritopic ligand derived from natural bile acid, ursodeoxycholic acid. We show that via the supramolecular transmetalation reaction, using nitrates of Cu(II) or Fe(III), and subsequently Pd(II), a superchiral Pd3L6complex can be obtained. Even though several possible constitutional isomers of Pd3L6could be formed, because of the ligand asymmetry and relative flexibility of carbamate-pyridyl moieties attached to the steroid scaffold, only a single product withC3rotational symmetry was obtained. Finally, we demonstrate that these amphiphilic complexes can self-organize into hexagonal microparticles in aqueous media. This finding may lead to the development of novel self-assembled metal-organic functional materials made of natural, abundant, and relatively inexpensive steroidal compounds.