Synthesis and characterization of bis (acetylacetonato κ-O, O′) [zinc(ii)/copper(ii)] hybrid organic–inorganic complexes as solid metal organic precursors

Abstract

We have synthesized novel metal organic hybrid mixed compounds of bis (acetylacetonato κ-O, O′) [zinc(II)/copper(II)]. Taking C₁₀H₁₄O₄Zn_0.7Cu_0.3 (Z_0.7C_0.3AA) as an example, the crystals are composed of Z_0.7C_0.3AA units and uncoordinated water molecules. Single-crystal X-ray diffraction results show that the complex Z_0.7C_0.3AA crystallizes in the monoclinic system, space group P2₁/n. The unit cell dimensions are a = 10.329(4) Å, b = 4.6947(18) Å, and c = 11.369(4) Å; the angles are α = 90°, β = 91.881(6)°, and γ = 90°, the volume is 551.0(4) ų, and Z = 2. In this process, the M(II) ions of Zn and Cu mix and occupy the centers of symmetrical structural units, which are coordinated to two ligands. The measured bond lengths and angles of O–M–O vary with the ratio of metal species over the entire series of the complexes synthesized. The chemistry of the as-synthesized compounds has been characterized using infrared spectroscopy, mass spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis, and the morphology of the products has been characterized using scanning electron microscopy. The thermal decomposition of the Z_0.7C_0.3AA composites measured by thermogravimetric analysis suggests that these complexes are volatile. The thermal characteristics of these complexes make them attractive precursors for metal organic chemical vapor deposition.