Crystal growth and structural motifs of luminescent PrCl3·ROH complexes: Molecular adducts and 1-D chains of tetradecanuclear rings

Pr2Cl6(CH3OH)8 (1), Pr2Cl6((CH3)2CHOH)8 (2) and (PrCl3)7(CH3CH2CH2OH)18·(CH3CH2CH2OH) (3) were synthesized via slow evaporation of a supersaturated solution of PrCl3 in methanol, isopropanol and n-propanol respectively. The crystal structures were determined, revealing two very different topological arrangements. The evaporation in the presence of methanol and isopropanol lead to dimeric molecular adducts, while n-propanol leads to the formation of 1-D chains of tetradecanuclear rings. The molecular adducts are held together via edge sharing polyhedra while the rings are held together via edge- and face-sharing polyhedra. The absorbance and luminescence of these compounds was also investigated.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Three novel structures incorporating PrCl3, in dimeric adducts or 1-D polymeric chains of rings. ► Topological control via the coordinating crystallization solvent, yielding unique topologies. ► Tetradecanuclear ring structure incorporating 14 Pr (III) cations via bridging chloride anions. ► Absorbance measurements suggest, that these species may be forming in solution at higher concentrations. ► Three luminescent compounds, optical properties investigated.