Imposing control on self-assembly: rational design and synthesis of a mixed-metal, mixed-ligand coordination cage containing four types of component.

Imposing control on self-assembly: rational design and synthesis of a mixed-metal, mixed-ligand coordination cage containing four types of component.
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DOI:
10.1039/c5sc03526k
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发表时间:
2016-02-01
期刊:
影响因子:
8.4
通讯作者:
Ward MD
Ward MD
中科院分区:
化学1区
文献类型:
--
作者:
Metherell AJ;Ward MD

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使用动力学惰性和动力学不稳定组分的组合的逐步组装方法允许基于四种类型的组分形成配位笼,其中每种组分指向特定位点。[M16 L24]32+配位笼的逆合成分析显示了如何使用动力学惰性和动力学不稳定组分的组合以逐步方式合理组装。fac-[Ru(Lph)3](PF 6)2、Cd(BF 4)2和Lnaph的组分以必要的4:12:得到[Ru 4Cd 12(Lph)12(Lnaph)12]X32晶体(X =单阴离子),其中两种类型的金属离子[Ru(ii)或Cd(ii)]在金属离子阵列中的特定顶点处的位置,以及两种类型的桥连配体(Lph和Lnaph)沿沿着特定的边缘,完全由合成策略控制。将四种不同类型的组件在预定的位置在一个协调笼的超结构中,代表了一个实质性的进步,施加控制复杂的金属超分子实体的自组装。
A stepwise assembly method, using a combination of kinetically inert and kinetically labile components, allows formation of a coordination cage based on four types of component with each component directed to a specific site. Retrosynthetic analysis of a [M16L24]32+ coordination cage shows how it can be assembled rationally, in a stepwise manner, using a combination of kinetically inert and kinetically labile components. Combination of the components of fac-[Ru(Lph)3](PF6)2, Cd(BF4)2 and Lnaph in the necessary 4 : 12 : 12 stoichiometry afforded crystals of [Ru4Cd12(Lph)12(Lnaph)12]X32 (X = a mono-anion) in which the location of the two types of metal ion [Ru(ii) or Cd(ii)] at specific vertices in the metal-ion array, and the two types of bridging ligand (Lph and Lnaph) along specific edges, is completely controlled by the synthetic strategy. The incorporation of four different types of component at pre-determined positions in a coordination cage superstructure represents a substantial advance in imposing control on the self-assembly of complex metallosupramolecular entities.
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