Understanding
the stability and speciation of metal-oxo clusters
in solution is essential for many of their applications in different
areas. In particular, hybrid organic–inorganic polyoxometalates
(HPOMs) have been attracting increasing attention as they combine
the complementary properties of organic ligands and metal–oxygen
nanoclusters. Nevertheless, the speciation and solution behavior of
HPOMs have been scarcely investigated. Hence, in this work, a series
of HPOMs based on the archetypical Anderson–Evans structure,
δ-[MnMo6O18{(OCH2)3C–R}2]3–, with different functional
groups (R = −NH2, −CH3, −NHCOCH2Cl, −NCH(2-C5H4N) {pyridine;
−Pyr}, and −NHCOC9H15N2OS {biotin; −Biot}) and countercations (tetrabutylammonium
{TBA}, Li, Na, and K) were synthesized, and their solution behavior
was studied in detail. In aqueous solutions, decomposition of HPOMs
into the free organic ligand, [MoO4]2–, and free Mn3+ was observed over time and was shown to
be highly dependent on the pH, temperature, and nature of the ligand
functional group but largely independent of ionic strength or the
nature of the countercation. Furthermore, hydrolysis of the amide
and imine bonds often present in postfunctionalized HPOMs was also
observed. Hence, HPOMs were shown to exhibit highly dynamic behavior
in solution, which needs to be carefully considered when designing
HPOMs, particularly for biological applications.