An organometallic nanosized capsule consisting of cyclo-P5 units and copper(I) ions.
An organometallic nanosized capsule consisting of cyclo-P5 units and copper(I) ions.
复制标题
由环P5单元和铜(I)离子组成的有机金属纳米胶囊
DOI：
10.1002/anie.201005910
复制
发表时间：
2011
影响因子：
--
通讯作者：
M. Scheer
中科院分区：
文献类型：
--
作者：
S. Welsch;C. Gröger;M. Sierka;M. Scheer
分子胶囊的组装是当前化学领域一个引人入胜且持续发展的课题。根据它们的大小和组成，分子胶囊可以作为特定客体分子的反应容器和超分子容器大多数已报道的系统是由有机寡聚基团（N， O和S连接体）构建的，这些连接体通过基于氢键或配位的互补相互作用连接到刘易斯酸性金属有时，宿主分子和客体分子之间的π堆积和CH··π相互作用在这种有机结构中起着重要作用对于无机系统，已知的是胶囊状金属配体聚集体，其中过渡金属的多金属氧酸盐[4]和最近的主要金属基团如硫化锡[5]已被有机连接分子连接起来。完全无机胶囊只描述了多金属氧酸盐。这些共价结合的体系可以作为具有柔性多孔表面的分子容器。[4d， 6]相比之下，迄今为止还没有空腔体之间具有弱非共价相互作用的有机金属胶囊的报道。最近，我们证明了有机金属多磷配体配合物用于球形富勒烯类超分子的自组装的潜力。本文采用环- p5配体配合物[Cp* Fe-(η5-P5)](1; Cp*= η5-C5Me5)[7]和环- p4配体配合物[Cp”Ta (CO2)(η4-P4)]（Cp”= η5-C5H3tBu2-1, 3）作为铜(I)卤化物之间的连接单元。[8,9]聚合物[8]的热力学有利形成强烈依赖于反应条件，并且可以避免，因此只得到球形超分子在所有这些化合物中，[Cp* Fe (η - 5- p5)]的环- p5配体作为五重对称的构建块，导致与富勒烯相似的结构基序。相比之下，我们现在发现，通过溶剂的变化，更重要的是，化学计量学，一种新的三重对称聚集发生，导致形成一个胶囊状的纳米级超分子主聚集体，在两个弱相关的半壳腔体中包含两个1的客体配合物。一般来说，原料的浓度在不溶性聚合物（浓度为> - 15 mmol LÀ1）或球形可溶性产物（浓度< 15 mmol LÀ1）的形成中起决定性作用。此外，卤化物的性质影响了不同聚合物的形成（2D为X= Br, I: 1,2,4的环- p5环1的配位模式（A，图1a）和1D为X= Cl: 1,2的配位模式（B，图1a））和90顶点球1@[{1}12-]的形成
The assembly of molecular capsules is a fascinating and ongoing topic in current chemistry. Depending on their size and composition, molecular capsules can serve as reaction vessels and supramolecular containers for specific guest molecules.[1] The majority of reported systems are built from organic oligotopic moieties (N, O, and S linkers) that are connected by complementary interactions based on hydrogen bonding or coordination to Lewis acidic metals.[2] Sometimes π-stacking and CH··· π interactions between host and guest molecules play an important role for such organic building blocks.[3] For inorganic systems, capsulelike metal–ligand aggregates are known, in which polyoxometalates of transition metals,[4] and, more recently, main-group-metal moieties such as tin sulfides [5] have been connected by organic linker molecules. Completely inorganic capsules have been described only for polyoxometalates. These covalently bound systems can act as molecular containers with flexible porous surfaces.[4d, 6] In contrast, no organometallic capsules with weak noncovalent interactions between the cavitands have been reported to date. Recently, we demonstrated the potential of organometallic polyphosphorus donor ligand complexes for the self-assembly of spherical fullerene-like supramolecules. Here, the cyclo-P5 ligand complex [Cp* Fe-(η5-P5)](1; Cp*= η5-C5Me5)[7] and the cyclo-P4 ligand complex [Cp’’Ta (CO2)(η4-P4)](Cp’’= η5-C5H3tBu2-1, 3) were used as linking units between copper (I) halides.[8, 9] The thermodynamically favored formation of polymers [8] is strongly dependent on the reaction conditions, and can be avoided so that only spherical supramolecules are obtained.[9] In all of these compounds, the cyclo-P5 ligand of [Cp* Fe (η5-P5)] serves as a fivefold symmetric building block that leads to structural motifs similar to those of the fullerenes. In contrast, we have now found that by variation of solvents and, more importantly, the stoichiometry, a novel threefold symmetric aggregation occurs that results in the formation of a capsulelike nanosized supramolecular host aggregate incorporating two guest complexes of 1 within two weakly associated half-shell cavitands.In general, the concentration of the starting materials plays a decisive role in the formation of either insoluble polymers (concentrations> 15 mmol LÀ1) or spherical soluble products (concentrations< 15 mmol LÀ1). Moreover, the nature of the halide influences the formation of different polymers (2D for X= Br, I: 1, 2, 4 coordination mode of cyclo-P5 ring of 1 (A, Figure 1a) and 1D for X= Cl: 1, 2 coordination mode (B, Figure 1a)) and of the 90-vertex ball 1@[{1} 12-
登录
查看更多内容
影响因子：
--
作者：
M. Scheer;Andrea Schindler;J. Bai;Brian P. Johnson;R. Merkle;R. Winter;A. Virovets;E. Peresypkina;V. Blatov;M. Sierka;H. Eckert
通讯作者：
M. Scheer;Andrea Schindler;J. Bai;Brian P. Johnson;R. Merkle;R. Winter;A. Virovets;E. Peresypkina;V. Blatov;M. Sierka;H. Eckert
自组装胶囊中的气体行为。
影响因子：
--
作者：
D. Ajami;J. Rebek
通讯作者：
J. Rebek
影响因子：
16.6
作者：
Scheer, Manfred;Schindler, Andrea;Peresypkina, Eugenia V.
通讯作者：
Peresypkina, Eugenia V.
绿色和西斯林盖恩海登的斯帕里斯集群
影响因子：
--
作者：
Brian P. Johnson;Fabian Dielmann;G. Balázs;Marek Sierka;M. Scheer
通讯作者：
M. Scheer
通过五磷杂二茂铁与银 (I) 阳离子配位可逆形成聚合物链。
影响因子：
--
作者：
M. Scheer;L. Gregoriades;A. Virovets;W. Kunz;R. Neueder;I. Krossing
通讯作者：
I. Krossing