Synthesis, structure and thermal behavior of volatile mononuclear mixed ligand complexes of rare-earth dipivaloylmethanates with diethylenetriamine

Abstract

Highly volatile and stable complexes of rare-earth elements with mononuclear structure are of great importance for gas phase deposition of functional thin film materials. Mixed ligand complexes with β-diketonate anions (e.g. thd− = 2,2,6,6-tetrametylheptane-3,5-dionate) and ancillary neutral donor ligands demonstrate mononuclear structure and sufficient volatility, however, they are unstable to neutral ligand elimination especially in case of light rare earth elements. Here diethylenetriamine (deta) has been applied as tridentate neutral ligand to improve the stability of mixed ligand complexes due to macrochelate effect and additional weak intramolecular interactions, e.g. hydrogen bonds. Synthesis of a series of mixed-ligand [Ln(thd)3(deta)], Ln = La (1L), Pr (2L), Nd (3L), Sm (4L) and Gd (5L) complexes, their X-ray single crystal structure characterization, DFT calculations, and thermal behavior study have been performed. Compounds 1L-5L demonstrate similar mononuclear molecular structure, but different molecular packing of three types, which may undergo mutual transformation. Compounds 1L-4L sublime intact in temperature range of 140–160 °C in vacuum without decomposition. 1L was successfully applied as volatile precursors for MOCVD preparation of epitaxial complex oxide thin films, (0 0 l) LaMnO3 and (0 0 l) LaAlO3, on (0 0 l) MgO and (0 0 l) SrTiO3 substrates.