Versatile post-functionalisation strategy for the formation of modular organic–inorganic polyoxometalate hybrids

Hybrid structures incorporating different organic and inorganic constituents are emerging as a very promising class of materials since they synergistically combine the complementary and diverse properties of the individual components. Hybrid materials based on polyoxometalate clusters (POMs) are particularly interesting due to their versatile catalytic, redox, electronic, and magnetic properties, yet the controlled incorporation of different clusters into a hybrid structure is challenging and has been scarcely reported. Herein we propose a novel and general strategy for combining multiple types of metal-oxo clusters in a single hybrid molecule. Two novel hybrid POM structures (HPOMs) bis-functionalised with dipentaerythritol (R–POM(1)–R; R = (OCH(2))(3)CCH(2)OCH(2)C(CH(2)OH)) were synthesised as building-blocks for the formation of heterometallic hybrid triads (POM(2)–R–POM(1)–R–POM(2)). Such a modular approach resulted in the formation of four novel heterometallic hybrids combing the Lindqvist {V(6)}, Anderson–Evans {XMo(6)} (X = Cr or Al) and trisubstituted Wells–Dawson {P(2)V(3)W(15)} POM structures. Their formation was confirmed by multinuclear Nuclear Magnetic Resonance (NMR), infrared (IR) and UV-Vis spectroscopy, as well as Mass Spectrometry, Diffusion Ordered Spectroscopy (DOSY) and elemental analysis. The thermal stability of the hybrids was also examined by Thermogravimetric Analysis (TGA), which showed that the HPOM triads exhibit higher thermal stability than comparable hybrid structures containing only one type of POM. The one-pot synthesis of these novel compounds was achieved in high yields in aqueous and organic media under simple reflux conditions, without the need of any additives, and could be translated to create other hybrid materials based on a variety of metal-oxo cluster building-blocks.