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. 2023 Apr 25;14(20):5405-5414.
doi: 10.1039/d3sc00038a. eCollection 2023 May 24.

Rational synthesis of elusive organic-inorganic hybrid metal-oxo clusters: formation and post-functionalization of hexavanadates

David E Salazar Marcano  1 , Givi Kalandia  1 , Mhamad Aly Moussawi  1 , Kristof Van Hecke  2 , Tatjana N Parac-Vogt  1
Affiliations

Rational synthesis of elusive organic-inorganic hybrid metal-oxo clusters: formation and post-functionalization of hexavanadates

David E Salazar Marcano et al. Chem Sci. .

Abstract

Paving the way towards new functional materials relies increasingly on the challenging task of forming organic-inorganic hybrid compounds. In that regard, discrete atomically-precise metal-oxo nanoclusters have received increasing attention due to the wide range of organic moieties that can be grafted onto them through functionalization reactions. The Lindqvist hexavanadate family of clusters, such as [V6O13{(OCH2)3C-R}2]2- (V6-R), is particularly interesting due to the magnetic, redox, and catalytic properties of these clusters. However, compared to other metal-oxo cluster types, V6-R clusters have been less extensively explored, which is mainly due to poorly understood synthetic challenges and the limited number of viable post-functionalization strategies. In this work, we present an in-depth investigation of the factors that influence the formation of hybrid hexavanadates (V6-R HPOMs) and leverage this knowledge to develop [V6O13{(OCH2)3CNHCOCH2Cl}2]2- (V6-Cl) as a new and tunable platform for the facile formation of discrete hybrid structures based on metal-oxo clusters in relatively high yields. Moreover, we showcase the versatility of the V6-Cl platform through its post-functionalization via nucleophilic substitution with various carboxylic acids of differing complexity and with functionalities that are relevant in multiple disciplines, such as supramolecular chemistry and biochemistry. Hence, V6-Cl was shown to be a straightforward and versatile starting point for the formation of functional supramolecular structures or other hybrid materials, thereby enabling their exploration in various fields.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Synthesis of hexavanadate post-functionalization platforms starting from V10 and triol ligands with reactive terminal groups.
Scheme 2
Scheme 2. Speciation of V10 in ACN after heating at 80 °C for 0–24 h: (a) alone or with (b) Tris-CH3, (c) Tris-NH2 or (d) Tris-Cl.
Fig. 1
Fig. 1. UV-vis-NIR absorbance spectra of V10 with (a) Tris-CH3, (b) Tris-NH2, or (c) Tris-Cl after 0 h at room temperature (r.t.) and after 0.5, 24, and 120 h at 80 °C, with the broad IVCT peak shown in the insert.
Fig. 2
Fig. 2. (a) Synthesis of V6-Cl from V10 and Tris-Cl along with the corresponding 1H NMR spectra of aliquots of the reaction mixture after heating at 80 °C for 0 and 20 h in (b) DMA or (c) ACN. All spectra were acquired for solutions in ACN-d3 of the precipitate formed by addition of excess of diethyl ether to the aliquot.
Fig. 3
Fig. 3. (a) CV of 0.5 mM V6-Cl in ACN vs. in DMA with 0.1 M TBA-PF6 as the electrolyte (100 mV s−1). (b) Structural representation of V6-Cl viewed along the crystallographic b axis and (c) crystal packing of V6-Cl into a 1D H-bond network (H-bond distances shown as dashed grey lines). The counter ions were omitted from the structural representations for clarity. Hydrogen in white, carbon in brown, nitrogen in light blue, oxygen in red, chlorine in green and vanadium in orange.
Fig. 4
Fig. 4. (a) 1H NMR spectrum of V6-Cl in DMSO-d6 as well as (b) negative mode and (c) positive mode ESI-MS spectra of V6-Cl in ACN.
Scheme 3
Scheme 3. Post-functionalization of V6-Clvia nucleophilic substitution with valeric acid, phenylacetic acid, adamantanecarboxylic acid, and biotin to form V6-Val, V6-Ph, V6-Ad, and V6-Biot (top to bottom).
Fig. 5
Fig. 5. (a) Structural representation of V6-Val showcasing the relative position of the CHCl3 and TBA molecules with respect to V6-Val in the crystal structure (two of each per hexavanadate unit that are symmetrically equivalent). (b) Crystal packing of V6-Val into a 1D H-bond network (H-bond distances shown as dashed grey lines) viewed along the crystallographic b axis without showing the TBA counter ions and CHCl3 for clarity. Hydrogen in white, carbon in brown, nitrogen in light blue, oxygen in red, chlorine in green and vanadium in orange.
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