Inorganic Borate Functionalized {<b>Ni<sub>6</sub>SiW<sub>9</sub></b>} Polyoxometalates: From Cluster to Cage Cluster
In aqueous solution systems, an all-inorganic Ni<sub>6</sub>-added polyoxometalate (Ni<sub>6</sub>AP) [Ni<sub>6</sub>(μ<sub>3</sub>–OH)<sub>3</sub>(H<sub>2</sub>O)<sub>12</sub>(B-α-SiW<sub>9</sub>O<sub>34</sub>)]<sup>1–</sup> ({<b>Ni</b><sub><b>6</b></sub><b>SiW</b><sub><b>9</b></sub>}, here, {<b>Ni</b><sub><b>6</b></sub>} = Ni<sub>6</sub>(μ<sub>3</sub>–OH)<sub>3</sub>(H<sub>2</sub>O)<sub>12</sub>) has been made via a hydrothermal method. By introducing inorganic boron sources, a B<sub>3</sub>O<sub>3</sub>(OH)<sub>6</sub> ({<b>B</b><sub><b>3</b></sub>}) cluster was precisely anchored onto {<b>Ni</b><sub><b>6</b></sub>} to form a [B<sub>3</sub>O<sub>3</sub>(OH)<sub>6</sub>Ni<sub>6</sub>(μ<sub>3</sub>–OH)<sub>2</sub>(H<sub>2</sub>O)<sub>8</sub>(B-α-SiW<sub>9</sub>O<sub>34</sub>)]<sup>3–</sup> ({<b>B</b><sub><b>3</b></sub>Ni<sub>6</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>8</sub><b>SiW</b><sub><b>9</b></sub>}) through replacing four terminal water molecules and condensing with one hydroxyl of the {<b>Ni</b><sub><b>6</b></sub>} cluster. Subsequently, the addition of further boron sources facilitated the in situ growth of B–O clusters on the basis of {<b>B</b><sub><b>3</b></sub>Ni<sub>6</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>8</sub><b>SiW</b><sub><b>9</b></sub>}, which resulted in the successful synthesis of {[B<sub>7</sub>O<sub>8</sub>O<sub>2/3</sub>(OH)<sub>6</sub>Ni<sub>6</sub>(μ<sub>3</sub>–OH)<sub>2</sub>(H<sub>2</sub>O)<sub>8</sub>(B-α-SiW<sub>9</sub>O<sub>34</sub>)]<sub>3</sub>}<sup>7–</sup> ({<b>B</b><sub><b>7</b></sub>Ni<sub>6</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>8</sub><b>SiW</b><sub><b>9</b></sub>}<sub>3</sub> or {<b>B</b><sub><b>21</b></sub>}@{Ni<sub>6</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>8</sub><b>SiW</b><sub><b>9</b></sub>}<sub>3</sub>). It is the first all-inorganic cage cluster constructed by NiAPs and B–O clusters, which successfully realizes the inorganic borate functionalized POMs from a single cluster to a cage cluster. The central {B<sub>7</sub>O<sub>8</sub>O<sub>2/3</sub>(OH)<sub>6</sub>}<sub>3</sub> ({<b>B</b><sub><b>21</b></sub>}) cluster exhibits an uncommon cavity configuration. Meanwhile, we have conducted a discussion of the possible formation mechanism of B–O functionalized NiAPs. Furthermore, these three compounds efficiently accelerate the oxidative transformation of sulfides, and the number of B atoms in compounds relatively affects the selectivity of the products.
Publication Details
- Journal
- Figshare
- Published
- 2025-03-03
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c05460.s001
- Primary Topic
- Mycorrhizal Fungi and Plant Interactions
- Type
- article
- Field-Weighted Citation Impact
- 0.00