Solvent‐Controlled Construction of Molecular Chains and Bowls/Sieves from a Bent Dipyridyl Ligand†

Abstract

Main observation and conclusionSolvothermal reactions of 3,6‐di(pyridin‐4‐yl)‐9H‐carbazole (dpc) with Cu(II) yielded crystals of two new coordination complexes, namely [Cu(CH3COO)2(dpc)(H2O)2]n·xGuest (1) and [Cu13(HCOO)16(dpc)16(H2O)6](HCOO)10·Guest (2), in which CH3COO– and HCOO– were generated from the hydrolysis of the solvents N,N‐dimethylacetamide (DMA) and N,N‐dimethylformamide (DMF), respectively. Single‐crystal X‐ray diffraction showed that 1 possesses simple wavy coordination chains, while 2 possesses large molecular bowls/sieves with outer and inner effective sizes of 30.2 × 30.2 × 25.5 Å3 and 15.0 × 15.0 × 18.6 Å3, respectively, which consists of 4 linear Cu3(HCOO)4(H2O) clusters and 12 dpc ligands as the square‐shaped wall and a claw‐like Cu(dpc)4 fragment as the bottle. Guest‐free 2 can adsorb considerable amounts of CO2, H2O and CH3OH but completely exclude C2H4 and C3H6, which shows a potential application for olefin drying.