The Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Inorg Chem. 2012 Mar 19;51(6):3860-7. doi: 10.1021/ic3000679. Epub 2012 Mar 2.
We report herein the synthesis of a new heteracalixaromatic compound, tetramethylazacalix[4]pyrazine (TAPz), and its coordination self-assemblies with metal and metal cluster centers. Structural characterization of TAPz has shown that its conformation is fluxional in solution but exhibits a dominant 1,3-alternate configuration in the crystalline solid state, wherein its convergent chelating coordination sites are orthogonal to the 120°-angled bridging sites, thus forming a unique multimodal ligand. Compound TAPz reacting with silver, zinc metal centers, and Cu(x)I(x) cluster centers leads to the construction of diverse coordination network structures in 1-5 including honeycomb, Kagomé, α-quartz, and cavity-involved two-dimensional layers. The structural diversity of these network structures is conducted by different combination modes between the chelation bonding sites of TAPz and metal or metal cluster centers. This system may afford deeper insight on the fantastic use of macrocyclic compounds on the designed synthesis of coordination network structures through the proper arrangement of their coordination sites.
我们在此报告了一种新的杂杯芳烃化合物，四甲基氮杂杯[4]吡嗪（TAPz）及其与金属和金属簇中心的配位自组装。TAPz 的结构表征表明，其构象在溶液中是易变的，但在晶体固体状态下表现出主要的 1,3-交替构型，其中其会聚螯合配位位点与 120°角桥接位点正交，从而形成独特的多模态配体。TAPz 与银、锌金属中心以及 Cu(x)I(x)簇中心反应，导致 1-5 中形成了各种配位网络结构，包括蜂窝状、Kagomé、α-石英和涉及空腔的二维层。这些网络结构的结构多样性是通过 TAPz 的螯合键合位点与金属或金属簇中心之间的不同组合模式来实现的。通过适当排列其配位位点，该体系可以为通过大环化合物在配位网络结构的设计合成中进行奇妙应用提供更深入的了解。
