Self-assembly of metal–organic coordination polymers occurs because of enthalpically favorable interactions. In the case of the bulky 4,4′-(anthracene-9,10-diyl)dibenzoic acid ligand (abdH2), we demonstrate that the presence of numerous π–π and C—H...π interactions outweigh the formation of saturated coordination complexes with zinc, leading to the formation of a dimethylformamide (DMF) solvate, namely 4,4′-(anthracene-9,10-diyl)dibenzoic acid dimethylformamide disolvate, C28H18O4·2C3H7NO or [(abdH2)(DMF)2], at low concentrations of zinc. Meanwhile, at higher zinc concentrations, the abdH2 ligand gives rise to the nonporous one-dimensional coordination polymer catena-poly[[bis(dimethylformamide-κO)zinc(II)]-μ-4,4′-(anthracene-9,10-diyl)dibenzoato-κ2
O:O′], [Zn(C28H16O4)(C3H7NO)2]
n
or [Zn(abd)(DMF)2]
n
, when assembled in dimethylformamide, while a related compound is observed when N,N-dimethylacetamide (DMA) is used as the solvent, namely catena-poly[[[bis(N,N-dimethylacetamide-κO)zinc(II)]-μ-4,4′-(anthracene-9,10-diyl)dibenzoato-κ2
O:O′] N,N-dimethylacetamide monosolvate], {[Zn(C28H16O4)(C4H9NO)2]·C4H9NO}
n
or {[Zn(abd)(DMA)2]·DMA}
n
. Attempts to use other amide-based solvents did not give rise to any other assembled structures.
Ligand and solvent effects in the formation and self-assembly of a metallosupramolecular cage