Trefoil-shaped metallacycle and metallacage via heteroleptic self-assembly

Template-oriented multi-component synthesis method has been proven to be an exceedingly reason-able 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 un-expected 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 cap-ping 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 ( 1 H NMR, 2D COSY, 2D NOESY, 2D DOSY), high-resolution electrospray ionization mass spectrometry ESI-MS, ESI-TWIM-MS, TEM and AFM. (c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.