Versatile Post-functionalisation Strategy for the Formation of Modular Organic-Inorganic Polyoxometalate Hybrids

26 November 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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 polyoxometalates (POMs) are particularly interesting due to the versatile catalytic, redox, electronic, and magnetic properties of this large family of metal-oxo clusters, yet the combination of different clusters has been scarcely reported. Hence, 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-POM1-R; R = (OCH2)3CCH2OCH2C(CH2OH)) were synthesised as building-blocks for the formation of heterometallic hybrid triads (POM2-R-POM1-R-POM2). Such a modular approach resulted in the formation of four novel heterometallic hybrids combing the Lindqvist {V6}, Anderson-Evans {XMo6} (X = Cr or Al) and trisubstituted Wells-Dawson {P2V3W15} 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. Their thermal stability was also examined by Thermogravimetric Analysis (TGA), which showed that overall 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 applied for creating other hybrid materials based on a variety of metal-oxo cluster building-blocks.


Hybrid materials
metal-oxo clusters

Supplementary materials

Versatile Post-functionalisation Strategy for the Formation of Modular Organic-Inorganic Polyoxometalate Hybrids Supplementary Information
Syntheses procedures for the formation of organic-inorganic polyoxometalate hybrid triads and their characterisation by Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared (FT-IR) spectroscopy, Mass Spectrometry (MS), Elemental Analysis, UV-Vis Spectroscopy and Single Crystal X-ray Diffraction (SC XRD).


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.