The synthesis of novel dinuclear lanthanide complexes with formulas [(LnL₃)(LiL)(MeOH)] (1–3) and [(LnL₃)(LiL)(H₂O)] (4–6) (Ln = Eu(III), Tb(III), Dy(III)) based on functionalized lithium β-diketonate (LiL) is reported. The coordination environment of the Ln(III) ion is formed by oxygen atoms of both the 1,3-dicarbonyl moiety and the acetal group. Depending on the solvent used for the crystallization, methanol or water molecules participate in the coordination with Li(I) ions affecting the crystal structure of complexes. In contrast to [(LnL₃)(LiL)(H₂O)] 4–6, a series of complexes [(LnL₃)(LiL)(MeOH)] 1–3 showed mechanoluminescence properties, thereby demonstrating the relationship between the observed optical properties and crystal packing architecture. The magnetic measurements of [(LnL₃)(LiL)(MeOH)] 1–3 revealed SMM behavior of [(DyL₃)(LiL)(MeOH)] 3 at low temperatures (U_eff is 37.7 cm⁻¹).

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.