Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional (2D) and three-dimensional (3D) supramolecules, but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge. Here we report two discrete trefoil-shaped metallacycle S1 and metallacage S2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands. The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic ‘Mitsubishi’ motif. The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2. The formed metallacage S2 possesses a molecular weight up to 36 kDa, diameter 6.6 nm and height 3.0 nm. All supramolecular coordination complexes were fully characterized by NMR spectroscopy (¹H NMR, 2D COSY, 2D NOESY, 2D DOSY), high-resolution electrospray ionization mass spectrometry ESI-MS, ESI-TWIM-MS, TEM and AFM.

面向模板的多组分合成方法已被证明是合成巨型二维（2D）和三维（3D）超分子的极其合理且优异的方法，但设计和构建杂配可控自组装无需意想不到的副产品仍然是一个挑战。在这里，我们使用一个六苯基苯核心配体和两个封端配体通过杂配自组装报告了两个离散的三叶形金属环S1和金属环S2 。二维三叶形金属周期S1可能类似于经典“三菱”图案的标志。模板导向配体和弯曲间隔配体的使用促进了所需3D三叶形金属基体S2的定量形成。形成的金属螯合物S2的分子量高达36 kDa，直径为6.6 nm，高度为3.0 nm。所有超分子配位配合物均通过 NMR 光谱（¹ H NMR、2D COSY、2D NOESY、2D DOSY）、高分辨率电喷雾电离质谱 ESI-MS、ESI-TWIM-MS、TEM 和 AFM 进行了全面表征。