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

Main observation and conclusion Solvothermal reactions of 3,6‐di(pyridin‐4‐yl)‐9 H ‐carbazole (dpc) with Cu(II) yielded crystals of two new coordination complexes, namely [Cu(CH 3 COO) 2 (dpc)(H 2 O) 2 ] n · x Guest (1) and [Cu 13 (HCOO) 16 (dpc) 16 (H 2 O) 6 ](HCOO) 10 ·Guest (2), in which CH 3 COO – 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 Å 3 and 15.0 × 15.0 × 18.6 Å 3 , respectively, which consists of 4 linear Cu 3 (HCOO) 4 (H 2 O) 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 CO 2 , H 2 O and CH 3 OH but completely exclude C 2 H 4 and C 3 H 6 , which shows a potential application for olefin drying.