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. 2022 Feb 8;13(10):2891-2899.
doi: 10.1039/d1sc06326j. eCollection 2022 Mar 9.

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

David E Salazar Marcano  1 , Mhamad Aly Moussawi  1 , Alexander V Anyushin  1 , Sarah Lentink  1 , Luc Van Meervelt  2 , Ivana Ivanović-Burmazović  3 , Tatjana N Parac-Vogt  1
Affiliations

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

David E Salazar Marcano et al. Chem Sci. .

Abstract

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-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. 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.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Representations of different hybrid polyoxometalate (HPOM) structures: (a) the bis-functionalised [V6O13{(OCH2)3C-R}2]2− Lindqvist hexavanadate, (b) the bis-functionalised δ-[{Xn+}M6O18{(OCH2)3C-R}2](6−n)− and (c) mono-functionalised δ-[{Xn+}(OH)3M6O18{(OCH2)3C-R}](6−n)− Anderson–Evans as well as (d) the mono-functionalised [P2V3W15O59{(OCH2)3C-R}]6− vanadium trisubstituted Wells–Dawson. Oxygen in red, vanadium in orange, metal addenda atom (Mo or W) in purple or grey, phosphorous in yellow, heteroatom X in magenta or cyan and organic carbon chain in skeletal form in black.
Fig. 2
Fig. 2. Reaction scheme showing the formation of [V6O13{(OCH2)3C-R}2]2− (L) and [CrMo6O18{(OCH2)3C-R}2]3− (C) functionalised with dipentaerythritol (R = CH2OCH2C(CH2OH)3) as building blocks for the formation of 4 heterogeneous POM–POM hybrids via post-functionalisation with [P2V3W15O62]9− (D) or [Al(OH)6Mo6O18]3− (A): DLD, DCD, ALA, ACA.
Fig. 3
Fig. 3. Mixed ball-stick and polyhedral representation of the structures of L (left) and C (right) as determined by single crystal X-ray diffraction. TBA counterions and the positional disorder were omitted for clarity.
Fig. 4
Fig. 4. Synthesis of DLD from L and D (top) and the corresponding 1H, 51V and 31P NMR spectra (bottom; ordered from left to right) of the POM–POM hybrid (black) and the starting materials (red for L and blue for D) illustrating the changes in the chemical shifts due to POM post-functionalisation of L.
Fig. 5
Fig. 5. Synthesis of DCD from C and D (top) together with the corresponding 51V and 31P NMR spectra (bottom left) of the POM–POM hybrid (black) and of D (blue) as well as the experimental and simulated cryo-MS spectra for DCD (bottom right).
Fig. 6
Fig. 6. Overlayed 1H 2D DOSY NMR spectra of L, ALA and DLD labelled with the translational diffusion coefficient (Ddiff) used to determine the hydrodynamic radius (r) for each structure, as shown on the right, and the corresponding 1H 1D NMR spectra shown at the top.
Fig. 7
Fig. 7. TGA profiles (top) showing the weight loss with increasing temperature for the building blocks, L and C, and their corresponding POM–POM hybrids: DLD, DCD, ALA, and ACA.
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