A Series of Lanthanide Complexes with Keggin-Type Monolacunary Phosphotungstate: Synthesis and Structural Characterization

The coordination of rare-earth metal ions (Ln3+) to polyoxometalates (POM) is regarded as a way of modifying and controlling their properties, such as single-molecular magnetism or luminescent behavior. The half-sandwich complexes of Ln3+ with monolacunary Keggin POMs (Ln3+/POM = 1:1) are of particular interest, since the Ln3+ retains its ability to coordinate extra ligands. Thus, the knowledge of the exact structures of 1:1 Ln/POM complexes is important for the development of reliable synthetic protocols for hybrid complexes. In this work, we isolated three 1:1 Gd3+/POM complexes of the general formula Cat4Gd(PW11O39)·xH2O (Cat = K+ or Me4N+). Complex (Me4N)2K2[Gd(H2O)2PW11O39]·5H2O (1) is polymeric, revealing a layered structural motif via bridging Gd3+ and K+ ions. Complexes (Me4N)6K2[Gd(H2O)3PW11O39]2·20H2O (2) and (Me4N)7K[Gd(H2O)3PW11O39]2·12H2O (3) are classified as dimeric; the difference between them consists of the different crystal packing of the polyoxometalates, which is induced by a variation in the cationic composition. Isostructural complexes have also been characterized for praseodymium, europium, terbium and dysprosium. The coordination number of Ln3+ (8) persists in all the compounds, while the binding mode of the POM varies, giving rise to different architectures with two or three H2O co-ligands per Ln3+. However, whatever the particular structure and exact composition, the {Ln(PW11O39)} moieties are always involved in bonding with each other with the formation either of polymeric chains or dimeric units. In water, these aggregates can dissociate with the formation of [Ln(H2O)4PW11O39]4-. This behavior must be taken into account when choosing L for the design of hybrid {Ln(L)POM} complexes.