Hydrothermal Synthesis and Characterization of Three Cationic Inorganic−Organic Hybrid Materials Based on Lead Fluoride

Three rare examples of extended inorganic materials possessing a cationic charge on the host have been successfully synthesized hydrothermally. The first structure consists of two-dimensional lead fluoride [Pb 9 F 16 ] 2+ sheets with perchlorate anions occupying the interlayer space. The material is a higher symmetry polytype of our previously reported lead fluoride nitrate Pb 3 F 5 ·NO 3 . Two new isoreticular layered metal−organic frameworks have also been discovered with cationic lead fluoride [Pb 2 F 2 ] 2+ layers pillared by 3- and 4-carbon chain alkylenedisulfonate molecules. Each structure was characterized by powder and single-crystal X-ray diffraction and thermogravimetric analysis. The thermal stability increases with the alkylene chain length of the linker molecule. The syntheses require the addition of perchloric acid to the reaction mixture. An improved synthesis for our previously reported lead fluoride polytype pillared by ethanedisulfonate in terms of increased yield and purity was also realized using perchloric acid.