Lead(II) acetate [Pb(Ac)2, where Ac = acetate group (CH3-COO(-))2] is a very common salt with many and varied uses throughout history. However, only lead(II) acetate trihydrate [Pb(Ac)2·3H2O] has been characterized to date. In this paper, two enantiotropic polymorphs of the anhydrous salt, a novel hydrate [lead(II) acetate hemihydrate: Pb(Ac)2·(1)/2H2O], and two decomposition products [corresponding to two different basic lead(II) acetates: Pb4O(Ac)6 and Pb2O(Ac)2] are reported, with their structures being solved for the first time. The compounds present a variety of molecular arrangements, being 2D or 1D coordination polymers. A thorough thermal analysis, by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), was also carried out to study the behavior and thermal data of the salt and its decomposition process, in inert and oxygenated atmospheres, identifying the phases and byproducts that appear. The complex thermal behavior of lead(II) acetate is now solved, finding the existence of another hydrate, two anhydrous enantiotropic polymorphs, and some byproducts. Moreover, some of them are phosphorescent at room temperature. The compounds were studied by TGA, DSC, X-ray diffraction, and UV-vis spectroscopy.
Short lead(II) alkanoates, from propionate to heptanoate, show a very intricate and reversible thermal behaviour, presenting crystalline phases and three different glass states (regular or amorphous, liquid crystal and rotator glasses) with different degrees of ordering depending on the alkyl chain length. A thorough thermal study was carried out in order to study the different phases and to analyze the thermodynamic parameters. The crystal structures of the compounds were solved by X-ray diffraction, showing similar arrangements of the 2D molecular stacking. PDF analyses of the local order in the glass structures showed shorter first neighbour lead-lead interatomic distances than in the crystalline structures. This allows establishment of a direct relationship between the structure and optical properties. Luminescence properties are, in fact, impressively enhanced in the glass states, passing from weak fluorescence at 77 K in the crystal phase to strong phosphorescence in the frozen glasses, which persists at room temperature. The high variability and the structure-property relationship described here pave the way for the design of materials with varied luminescence properties based on fine-tuning of their local structure.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.