Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University , Jinan 250100, P. R. China.
State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, P. R. China.
ACS Appl Mater Interfaces. 2017 Jun 14;9(23):19980-19987. doi: 10.1021/acsami.7b05191. Epub 2017 Jun 1.
A family of six triple-decker complexes, {(MX)[(pz)]} (Hpz = 4-nitropyrazole, MX = NaCl, 1; NaBr, 2; NaI, 3; KCl, 4; KBr, 5, and KI, 6), exhibiting inclusion of halides into inverse 12-metallacrown-4 [inv-(12-MC-4)] array has been realized. Single-crystal X-ray crystallography of each compound reveals a common structural feature consisting of four Cu ions bonded by four pz to form a square metallomacrocycle comprising four metal centers and eight N atoms, thus giving an inv-[12-MC-4] motif. Two halides are sandwiched by three inv-[12-MC-4] to form triple-deckers that are further extended in an offset stacking mode by ligand-unsupported cuprophilicity interactions to form a one-dimensional chain structure. Halides are attached to six Cu centers with weak Cu···halogen interaction, resembling anion templates. High-resolution electrospray ionization mass spectrometry reveals that the predominant fragments corresponding to a half of the triple-decker structures of 1-3 exist in solution. Compounds 4, 5, and 6 showed excellent electrocatalytic activities toward the reduction of nitrite and can also be used as selective "turn-off" sensors for Ag(I) in water. The present results will be helpful for the future design and synthesis of functional inverse metallacrowns and their multiple-decker complexes.
一个六元的夹心配合物家族，{(MX)[(pz)]}（Hpz = 4-硝基吡唑，MX = NaCl，1；NaBr，2；NaI，3；KCl，4；KBr，5，和 KI，6），实现了卤化物包入反式 12-金属冠-4 [inv-(12-MC-4)] 结构。每个化合物的单晶 X 射线晶体学揭示了一个共同的结构特征，由四个通过 pz 键合的 Cu 离子组成，形成一个由四个金属中心和八个 N 原子组成的正方形金属大环，从而给出了 inv-[12-MC-4] 基序。两个卤化物被三个 inv-[12-MC-4]夹在中间，形成夹心配合物，这些夹心配合物通过配体非支持的铜亲合相互作用以偏移堆积模式进一步扩展，形成一维链状结构。卤化物与六个 Cu 中心通过弱的 Cu···卤素相互作用连接，类似于阴离子模板。高分辨率电喷雾电离质谱显示，溶液中存在主要对应于 1-3 的夹心配合物结构的一半的片段。化合物 4、5 和 6 对亚硝酸盐的还原表现出优异的电催化活性，并且还可以用作水中 Ag(I)的选择性“关闭”传感器。本研究结果将有助于未来设计和合成功能性反式金属冠和它们的多夹心配合物。
