Supramolecular Interactions in PuO2Cl42– and PuCl62– Complexes with Protonated Pyridines: Synthesis, Crystal Structures, and Raman Spectroscopy

The synthesis, crystal structures, and Raman spectra of seven plutonium chloride compounds are presented. The materials are based upon Pu­(VI)­O2Cl42– and Pu­(IV)­Cl62– anions that are charge balanced by protonated pyridinium cations. The single crystal X-ray structures show a variety of donor–acceptor interactions between the plutonium perhalo anions and the cationic pyridine groups. Complementary Raman spectra show that these interactions can be probed through the symmetric vibrational mode of the plutonyl moiety. Unlike previously reported studies in similar uranyl­(VI) systems, the facile redox chemistry of plutonium in aqueous solution has demonstrated the feasibility of using not only the An­(VI)­O2Cl42– anion with approximate D4h symmetry but also the approximately Oh An­(IV)­Cl62– anion in order to manipulate both the structure and dimensionality of such hybrid materials.