Synthesis, structural, vibrational and DFT investigation of new binuclear molecular Pd–Cu and Cu–Cu complexes formed by Schiff base and hexafluoroacetylacetonate building blocks

Abstract

In this work, the first binuclear molecular noble metal-contained complex from the Schiff base (SB) and β-diketonate building blocks, viz. [Pd(acacen)Cu(hfac) 2 ], has been synthesized and investigated in comparison with the homometallic binuclear analog [Cu(acacen)Cu(hfac) 2 ]. A detailed comparative characterization of the structure of these new compounds as well as their molecular SB components [M(acacen)] was performed through crystallography, vibrational spectroscopy and DFT calculations. The experimental IR bands have been assigned on the basis of DFT calculations. The Hirshfeld surface analysis was used as a tool for better insight into intermolecular contacts. It has been shown that despite both bimetallic complexes have similar molecular structure and packing style, the nature of the closest intermolecular contacts in [M(acacen)Cu(hfac) 2 ] differs considerably. A topological analysis of the electron density distribution in [M(acacen)] and [M(acacen)Cu(hfac) 2 ] complexes was carried out and the most probable paths of bond cleavage upon decomposition of the compounds were revealed. The binding energies of the molecular components in binuclear complexes were also calculated.

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

“…In this case, the replacement of the bridging acetate anion by 1-pyrenbutanoic acid (complex 66, Figure 33) reduced the phosphorescence lifetime. The co-crystallization of copper(II) β-diketonate with palladium(II) bis-enaminoketonate led to the heterobimetallic [Cu-Pd] complex 67 [105]. The bridging oxygen atoms of bisenaminoketone between palladium(II) and copper(II) ions formed a discrete binuclear framework of the complex 67 (Figure 34).…”

“…The bridging oxygen atoms of bisenaminoketone between palladium(II) and copper(II) ions formed a discrete binuclear framework of the complex 67 (Figure 34). The co-crystallization of copper(II) β-diketonate with palladium(II) bis-enaminoketonate led to the heterobimetallic [Cu-Pd] complex 67 [105]. The bridging oxygen atoms of bis-enaminoketone between palladium(II) and copper(II) ions formed a discrete binuclear framework of the complex 67 (Figure 34).…”