Three Resorcin[4]arene-Based Two-Dimensional Zn(II) Supramolecular Isomers Synthesized via a Structure-Directing Strategy for Knoevenagel Condensation.

Herein, in the presence of three structure-directing agents (SDAs), a family of imidazole-functionalized resorcin[4]arene-based coordination polymers (CPs), [Zn(TIC4R)(HCOO)]·HCOO·0.5DMF·1.5H2O (1), [Zn(TIC4R)(CN)]·HCOO·DMF·2.5H2O (2), and [Zn(TIC4R)(H2O)]·2HCOO·2H2O (3), were assembled under solvothermal conditions [TIC4R = tetra(imidazole) resorcin[4]arene]. 1 exhibits a double-layer structure with rectangle windows, and 2 and 3 display monolayer structures. The layers of CPs 2 and 3 are slides with different offsets along the a-axis. In addition, three CPs were used as catalysts to catalyze Knoevenagel condensations. Strikingly, all CPs exhibit remarkable catalytic performance for several substrates. To the best of our knowledge, this is the first time that a small organic acid as SDA was used in the syntheses of resorcin[4]arene-based supramolecular isomers.