Synthesis, crystal-structure refinement and properties of bastnaesite-type PrF[CO3], SmF[CO3] and EuF[CO3]

By adding a hot aqueous solution containing KF and K2[CO3] to another hot aquatic brine of Pr[NO3]3 ⋅ 5 H2O, Sm[NO3]3 ⋅ 5 H2O or Eu[NO3]3 ⋅ 5 H2O with a 1.3 times excess of the anion-providing solution, amorphous water-insoluble powders of PrF[CO3], SmF[CO3] and EuF[CO3] can be obtained. Through hydrothermal treatment at 210 °C for five days crystalline powders could be synthesized and their crystal structure was refined with Rietveld methods based on PXRD data. The named compounds crystallize in the bastnaesite-type structure with a = 710.912(12) pm, c = 976.811(6) pm for the praseodymium, a = 704.77(2) pm, c = 971.83(4) pm for the samarium and a = 700.734(6) pm, c = 969.066(8) pm for the europium compound, all hexagonal with Z = 6. Upon heating them, the compounds lose CO2 and fluoride oxides REFO emerge. Thermogravimetric experiments with crystalline samples show thermal stability up to 420 °C for PrF[CO3], 400 °C for SmF[CO3] and 340 °C for EuF[CO3], but decomposition below 200 °C for the amorphous ones. Infrared spectroscopy confirms only marginal portions of [OH]− instead of F− anions in all cases. The RE 3+ cations are coordinated by 9 + 2 anions at distances between 236 and 254 pm plus 326 pm to F− anions and oxygen atoms bonded to carbon as oxocarbonate anions [CO3]2−. Triggered by ultraviolet radiation, the bulk sample of EuF[CO3] shows a poor red luminescence.

Gamma Radiation- and Ultraviolet-Induced Polymerization of Bis(amino acid)fumaramide Gel Assemblies

Controlling the polymerization of supramolecular self-assembly through external stimuli holds great potential for the development of responsive soft materials and manipulation at the nanoscale. Vinyl esters of bis(leu or val)fumaramide (1a and 2a) have been found to be gelators of various organic solvents and were applied in this investigation of the influence of organogelators’ self-assembly on solid-state polymerization induced by gamma and ultraviolet irradiation. Here, we report our investigation into the influences of self-assemblies of bis(amino acid vinyl ester)fumaramides on gamma-ray- and ultraviolet-induced polymerization. The gelator molecules self-assembled by non-covalent interactions, mainly through hydrogen bonds between the amide group (CONH) and the carboxyl group (COO), thus forming a gel network. NMR and FTIR spectroscopy were used to investigate and characterize supramolecular gels. TEM and SEM microscopy were used to investigate the morphology of gels and polymers. Morphology studies showed that the gels contained a filamentous structure of nanometer dimensions that was exhaustive in a three-dimensional network. The prepared derivatives contained reactive alkyl groups suitable for carrying out the polymerization reaction initiated by gamma or ultraviolet radiation in the supramolecular aggregates of selected gels. It was found that the polymerization reaction occurred only in the network of the gel and was dependent on the structure of aggregates or the proximity and orientation of double bonds in the gel network. Polymers were formed by the gels exposure to gamma and ultraviolet radiation in toluene, and water/DMF gels with transcripts of their gel structure into polymers. The polymeric material was able to immobilize various solvents by swelling. Furthermore, methyl esters of bis(leu and val)fumaramide (1b and 2b) were synthesized; these compounds showed no gelling properties, and the crystal structure of the valine derivative 2b was determined.