Bismuth Coordination Polymers with Fluorinated Linkers: Aqueous Stability, Bivolatility, and Adsorptive Behavior

Bismuth metal-organic frameworks and coordination polymers (CP) are challenging to synthesize, given the poor solubility of bismuth precursors and asymmetric and labile ligation of Bi³⁺ due to its intrinsic lone pair. Here, we synthesize and structurally characterize three Bi³⁺-CPs, exploiting a tetrafluoroterephtalate (F₄BDC) linker to determine the effect of high acidity on these synthesis and coordination challenges. Single-crystal X-ray diffraction characterization showed that pi-pi stacking of linkers directs framework arrangement and generally deters open porosity in the three structures, respectively featuring Bi chains (Bi _chain -F ₄ BDC), Bi dimers (Bi ₂ -F ₄ BDC) linked into chains, and Bi tetramers (Bi ₄ -F ₄ BDC). Powder X-ray diffraction and microscopic imaging show the high purity and stability of these compounds in water. Naphthalenedisulfonate (NDS) was used as a mineralizer in the synthesis of (Bi _chain -F ₄ BDC) and (Bi ₄ -F ₄ BDC), and studies of its role in assembly pathways yielded two additional structures featuring mixed NDS and F₄BDC, respectively, linking monomer and octamer Bi nodes, and confirmed that F₄BDC is the preferred (less labile) linker. Methylene blue (MB) adsorption studies show differing efficacies of the three Bi-F₄BDC phases, attributed to surface characteristics of the preferential growth facets, while generally most effective adsorption is attributed to the hydrophobicity of fluorinated ligands. Finally, thermogravimetric analysis of all three Bi-F₄BDC phases indicates simultaneous ligand degradation and in situ formation of volatile Bi compounds, which could be exploited in the chemical vapor deposition of Bi-containing thin films.