This review summarizes the data on the synthesis of coordination compounds containing two or more different metal ions based on fluorinated β-diketonates. Heterometallic systems are of high interest in terms of their potential use in catalysis, medicine and diagnostics, as well as in the development of effective sensor devices and functional materials. Having a rich history in coordination chemistry, fluorinated β-diketones are well-known ligands generating a wide variety of heterometallic complexes. In this context, we focused on both the synthetic approaches to β-dicarbonyl ligands with additional coordination centers and their possible transformations in complexation reactions. The review describes bi- and polynuclear structures in which β-diketones are the key building blocks in the formation of a heterometallic framework, including the examples of both homo- and heteroleptic complexes.

A convenient approach to substituted pyrazoles and pyridazinones based on 1,2,4-triketones is presented. Chemo- and regiocontrol in condensations of t-Bu, Ph-, 2-thienyl-, and CO₂Et-substituted 1,2,4-triketone analogs with hydrazines are described. The direction of preferential nucleophilic attack was shown to be switched depending on the substituent nature in triketone as well as the reaction conditions. The acid and temperature effects on the selectivity of condensations were revealed. Regiochemistry of heterocyclic core formation was confirmed by NMR and XRD studies. The facile construction of heterocyclic motifs bearing acetyl and (or) carbethoxy groups suggests them as promising mono- or bifunctional building blocks for subsequent transformations.

Functionalized perfluoroalkyl lithium β-diketonates (LiL) react with lanthanide(III) salts (Ln = Eu, Gd, Tb, Dy) in methanol to give heterobimetallic Ln-Li complexes of general formula [(LnL₃)(LiL)(MeOH)]. The length of fluoroalkyl substituent in ligand was found to affect the crystal packing of complexes. Photoluminescent and magnetic properties of heterobimetallic β-diketonates in the solid state are reported. The effect of the geometry of the [LnO₈] coordination environment of heterometallic β-diketonates on the luminescent properties (quantum yields, phosphorescence lifetimes for Eu, Tb, Dy complexes) and single-ion magnet behavior (U_eff for Dy complexes) is revealed.

The reaction of (perfluoroalkyl)furan-3(2H)-ones and β-diketone containing an acetal moiety with (hetero)aromatic 1,2-diamines was studied. Quinoxalines and pyrido[3,4-b]pyrazine bearing the enaminoketone fragment were ynthesized by the regioselective addition of a dinucleophile at the α-dicarbonyl moiety of polyketones. In the case of β-diketone containing acetal and ester groups, the conversion involves the α-ketoester moiety to form a quinoxalinyl-substituted 2,3-butanedione. All products were characterized by NMR spectroscopy and X-ray diffraction.

The similar properties of the nitrogen atoms in azole ring complicate the regioselective N-functionalization of pyrazoles. This work demonstrates the role of the hydrazone substituent in the control of the alkylation selectivity of (trifluoromethyl)pyrazoles. Reaction conditions for the synthesis of 3- and 5-(trifluoromethyl)pyrazoles were developed, and all types of regioisomers formed under the alkylation of bis-pyrazolyl NH-ketazine were isolated. The structures of the synthesized compounds were confirmed by NMR spectroscopy and XRD data.