Rings and Things: The Magic of Building Self-Assembled Cages and Macrocycles
Rings and Things: The Magic of Building Self-Assembled Cages and Macrocycles
复制标题
环和东西：建造自组装笼子和大环的魔力
DOI：
10.1021/acs.inorgchem.8b00553
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发表时间：
2017
影响因子：
4.6
通讯作者：
Hooley, Richard J.
中科院分区：
文献类型：
--
作者：
Hooley, Richard J.
使用金属介导的自组装来创建不同形状、大小和化学计量的多边形和多面体的概念在过去30年中得到了巨大的发展。1− 3通过自组装合成这些几何形状不同的化合物已经朝着功能化笼的创建方向发展，并朝着各种生物和材料应用的方向发展。例子包括分子机器和开关，5药物输送剂，6和仿生催化剂。7在本次论坛上，我们强调了自组装笼和大环化合物的合成和应用方面的最新进展。这里的许多论文描述了构建异多金属笼和其他复杂组件的方法。大多数已知的笼利用类似的概念，因为将单一金属和单一类型的刚性对称配位配体组合有利于特定的笼络合物，通常是最稳定的。这使研究人员能够克服将多个不同组件组合到一个组件中的熵惩罚。2用一种以上的金属构建笼是一项具有挑战性的任务，需要仔细规划以在组装过程中赋予选择性。例如，卢斯比、Piligkos、布雷钦及其同事阐述了用不同配位金属构建异质结笼的模块化策略。8当强配位配体1-（4-吡啶基）丁烷-1，3-二酮与Fe 3+离子结合时，可以形成离散的稳定金属配体，然后可以与正方形平面金属如Pd 2+结合形成Fe 8 Pd 6L 24化学计量的立方组装体。笼显示新的自旋交叉行为，和合成路线允许其他八面体金属以及引入。Lu Zhaotzen及其同事还利用一种逐步的模块化方法来构建异质结组装。在这种情况下，Fe 2+盐、tren配体和供体甲酰基吡啶的组合允许获得稳定的阳离子配位金属配体。这种含吡啶基的金属配体可以与各种Pd 2+盐组合以形成不同的组装类型，根据所使用的钯盐的性质，可以是三角双锥或立方笼。在这两种情况下，初始金属配体的稳定性允许控制整个组装过程。
The concept of using metal-mediated self-assembly to create polygons and polyhedra of different shapes, sizes, and stoichiometries has seen tremendous growth during the past 30 years. 1− 3 The synthesis of these geometrically diverse compounds via self-assembly has evolved toward the creation of functionalized cages 4 and their development toward various biological and materials applications. Examples include molecular machines and switches, 5 drug-delivery agents, 6 and biomimetic catalysts. 7 In this Forum, we have highlighted cutting-edge advances in the synthesis and application of selfassembled cages and macrocycles. A number of papers here describe methods to build heteropolymetallic cages and other complex assemblies. The majority of known cages exploit a similar concept, in that combining a single metal and a single type of rigid, symmetrical coordinating ligand favors a specific cage complex, usually the thermodynamically most stable. This allows researchers to overcome the entropic penalty of bringing together multiple different components into a single assembly. 2 The construction of cages with more than one type of metal is a challenging task, one that requires careful planning to confer selectivity in the assembly process.For example, Lusby, Piligkos, Brechin, and co-workers illustrate a modular strategy for constructing heterobimetallic cages with different coordinating metals. 8 When a strongly coordinating ligand, 1-(4-pyridyl) butane-1, 3-dione, is combined with Fe3+ ions, a discrete, stable metalloligand is possible, which can then be combined with square-planar metals such as Pd2+ to form cubic assemblies of Fe8Pd6L24 stoichiometry. The cages display novel spin-crossover behavior, and the synthetic route allows other octahedral metals to be introduced as well. Lützen and co-workers also exploit a stepwise, modular approach to construct heterobimetallic assemblies. 9 In this case, the combination of Fe2+ salts, tren ligands, and donor formylpyridines allows access to a stable, cationic coordinating metalloligand. This pyridyl-containing metalloligand can be combined with various Pd2+ salts to form different assembly types, either trigonal bipyramids or cubic cages, depending on the nature of the palladium salt used. In both cases, the stability of the initial metalloligand allows control of the overall assembly process.