Volatile Heterobimetallic Complexes from PdII and CuII β-Diketonates: Structure, Magnetic Anisotropy, and Thermal Properties Related to the Chemical Vapor Deposition of CuPd Thin Films.

Abstract

A novel approach for preparing volatile heterometallic complexes for use as precursors for the chemical vapor deposition of various materials is reported. New CuPd complexes based on β-diketonate units were prepared, and their structures and compositions were determined. [PdL2 *CuL2 ] (1) and [PdL2 *Cu(tmhd)2 ] (2) (L=2-methoxy-2,6,6-trimethylheptane-3,5-dionate; tmhd=2,2,6,6- tetramethylheptane-3,5-dionate) are 1D coordination polymers with alternating metal complexes, which are connected through weak interactions between the Cu atoms and the OCH3 groups from the ligand of the Pd complexes. The volatility and thermal stability were studied using thermogravimetric and differential thermal analyses and mass spectrometry. Compound 1 vaporizes without decomposition into monometallic complexes. It exhibits magnetic anisotropy, which was revealed from the angular variations in the EPR spectrum of a single crystal. The vapor thermolysis process for 1 was investigated using mass spectrometry, allowing the process to be framed within the temperature range of 200-350 °C. The experimental data, supported by QTAIM calculations of the allowed intermolecular interactions, suggest that 1 likely exists in the gas phase as bimetallic molecules. Compound 1 proved to be suitable as a single-source precursor for the efficient preparation of CuPd alloy films with tunable Cu/Pd ratio. A possible mechanism for the film growth is proposed based on the reported data.