Pascu Mirela, Tuna Floriana, Kolodziejczyk Edyta, Pascu Gabriel I, Clarkson Guy, Hannon Michael J
Centre for Supramolecular and Macromolecular Chemistry, Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, UK CV4 7AL.
Dalton Trans. 2004 May 21(10):1546-55. doi: 10.1039/b403749a. Epub 2004 Apr 21.
Aggregation of metallo-supramolecular architectures through additional coordination is explored by introducing metal-binding units onto the outside of the supramolecular architectures. This is achieved within the framework of our imine-based approach to supramolecular architecture, by replacing the pyridylimine units with pyrazylketimine units. An advantage of the design is that it retains the ease-of-synthesis which characterises our imine-based approach. Silver(I) complexes of three pyrazylketimine ligand systems are described. The complexes demonstrate that introducing pyrazine donor units does indeed allow higher-order assembly of the distinct supramolecular architectures into engineered coordination polymers. Two distinct types of aggregation are observed. In the first, the donors on the outside of one architecture bind to the metals of another to link the units into a polymeric array. In the second type, the donors on the outside of the architectures bind to separate metal centres which are themselves not part of the architectures, and these separate metal centres link the units to form the macromolecular array. The weaker donor nature of the pyrazine nitrogens (compared to pyridine) also introduces an additional element into the design; higher coordination numbers are favoured and this can lead to arrays with higher connectivity than those observed in the discrete pyridylimine architectures.
通过将金属结合单元引入超分子结构的外部,探索了通过额外配位实现金属超分子结构的聚集。这是在我们基于亚胺的超分子结构方法框架内实现的,通过用吡嗪基酮亚胺单元取代吡啶基亚胺单元。该设计的一个优点是它保留了我们基于亚胺的方法所具有的合成简便性。描述了三种吡嗪基酮亚胺配体体系的银(I)配合物。这些配合物表明,引入吡嗪供体单元确实允许将不同的超分子结构组装成工程化的配位聚合物。观察到两种不同类型的聚集。第一种情况是,一种结构外部的供体与另一种结构的金属结合,将单元连接成聚合物阵列。在第二种类型中,结构外部的供体与本身不是结构一部分的单独金属中心结合,这些单独的金属中心连接单元以形成大分子阵列。吡嗪氮(与吡啶相比)较弱的供体性质也为该设计引入了一个额外的因素;更倾向于高配位数,这可能导致比离散吡啶基亚胺结构中观察到的具有更高连接性的阵列。