One-dimensional networks formed via the self-assembly of anthracenedibenzoic acid with zinc(II)

Abstract

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-κ²O: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-κ²O: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.

Keywords: MOF; anthracene; crystal structure; dibenzoic acid; metal–organic framework; one-dimensional coordination polymer; self-assembly; zinc; π–π interactions.