Lewis James E M
Department of Chemistry, Imperial College London, Molecular Sciences Research Hub, 82 Wood Lane, London, W12 0BZ, UK.
Chemistry. 2021 Mar 1;27(13):4454-4460. doi: 10.1002/chem.202005363. Epub 2021 Feb 1.
Although many impressive metallo-supramolecular architectures have been reported, they tend towards high symmetry structures and avoid extraneous functionality to ensure high fidelity in the self-assembly process. This minimalist approach, however, limits the range of accessible structures and thus their potential applications. Herein is described the synthesis of a family of ditopic ligands wherein the ligand scaffolds are both low symmetry and incorporate exohedral functional moieties. Key to this design is the use of Cu -catalysed azide-alkyne cycloaddition (CuAAC) chemistry, as the triazole is capable of acting as both a coordinating heterocycle and a tether between the ligand framework and functional unit simultaneously. A common precursor was used to generate ligands with various functionalities, allowing control of electronic properties whilst maintaining the core structure of the resultant cis-Pd L nanocage assemblies. The isostructural nature of the scaffold frameworks enabled formation of combinatorial libraries from the self-assembly of ligand mixtures, generating a statistical mixture of multi-functional, low symmetry architectures.
尽管已经报道了许多令人印象深刻的金属超分子结构，但它们倾向于高对称结构，并避免引入无关的官能团以确保自组装过程的高保真度。然而，这种极简主义方法限制了可及结构的范围，从而限制了它们的潜在应用。本文描述了一类双齿配体的合成，其中配体支架具有低对称性并包含外表面功能部分。该设计的关键是使用铜催化的叠氮化物-炔烃环加成（CuAAC）化学，因为三唑能够同时作为配位杂环以及配体骨架与功能单元之间的连接基团。使用一种常见的前体来生成具有各种功能的配体，从而在保持所得顺式-Pd L纳米笼组装体核心结构的同时控制电子性质。支架框架的同构性质使得能够从配体混合物的自组装形成组合库，从而生成多功能、低对称结构的统计混合物。
