Diverse Coordination Chemistry of the Whole Series Rare-Earth L-Lactates: Synthetic Features, Crystal Structure, and Application in Chemical Solution Deposition of Ln2O3 Thin Films

Abstract

Rare-earth (RE, Ln) carboxylates are widely studied as precursors of RE oxide-based nanomaterials; however, no systematic studies of RE L-lactates (HLact = 2-hydroxypropanoic acid) have been reported to date. In the present work, a profound structural investigation of RE L-lactates is carried out. A family of RE lactate complexes of the general formula LnLact3∙nH2O (Ln = La, Ce–Nd, Sm–Lu, Y; n = 2–3) are synthesized and characterized by CHN, TGA, and FTIR as well as by powder and single-crystal XRD methods.The existence of four novel structural types (1-Ln–4-Ln) is revealed. Compounds of the 1-Ln type (Ln = La, Ce, Pr) exhibit a chain polymeric structure, whereas 2-Ln–4-Ln compounds are molecular crystals consisting of dimeric (2-Ln; Ln = La, Ce–Nd) or monomeric (3-Ln–Ln = Sm–Lu, Y; 4-Ln–Ln = Sm–Gd, Y) species. The crystal structures of 1-Ln–4-Ln compounds are discussed in terms of their coordination geometry and supramolecular arrangement. Solutions of yttrium and lanthanum lactates with diethylenetriamine are applied for the chemical deposition of Y2O3 and La2O3 thin films.

Polytypism and Packing-Dependent Colossal Positive and Negative Thermal Expansion in a 2D Layered Cerium-Based Coordination Polymer

“…The great majority of papers on polytypism are dedicated to inorganic systemsin particular, close-packed and layered compounds. − Much less attention is devoted to analogous phenomena among organic and metal–organic crystals, where weak intermolecular interactions may also give rise to the coexistence of different stacking motifs with comparable Gibbs free energies. A few examples of polytypism in such solids include some coordination polymers − and molecular compounds l -tryptophan, piracetam, octadecanoic acid, , mononuclear rare-earth (RE) complexes, and some others.…”