Authors: Cristiana Cesari | Beatrice Berti | Marco Bortoluzzi | Cristina Femoni | Tiziana Funaioli | Federico Maria Vivaldi | Maria Carmela Iapalucci | Stefano Zacchini
Source: Dalton Transactions (article, 2023-01-01)
Field: Materials Science — Materials Chemistry

From M<sub>6</sub> to M<sub>12</sub>, M<sub>19</sub> and M<sub>38</sub> molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters Heterometallic Chini-type clusters [Pt<sub>6-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>12</sub>]<sup>2-</sup> (<i>x</i> = 0-6) were obtained by reactions of [Pt<sub>6</sub>(CO)<sub>12</sub>]<sup>2-</sup> with Ni-clusters such as [Ni<sub>6</sub>(CO)<sub>12</sub>]<sup>2-</sup>, [Ni<sub>9</sub>(CO)<sub>18</sub>]<sup>2-</sup> and [H<sub>2</sub>Ni<sub>12</sub>(CO)<sub>21</sub>]<sup>2-</sup>, or from [Pt<sub>9</sub>(CO)<sub>18</sub>]<sup>2-</sup> and [Ni<sub>6</sub>(CO)<sub>12</sub>]<sup>2-</sup>. The Pt/Ni composition of [Pt<sub>6-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>12</sub>]<sup>2-</sup> (<i>x</i> = 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt<sub>9</sub>(CO)<sub>18</sub>]<sup>2-</sup> with [Ni<sub>9</sub>(CO)<sub>18</sub>]<sup>2-</sup> and [H<sub>2</sub>Ni<sub>12</sub>(CO)<sub>21</sub>]<sup>2-</sup>, as well as reactions of [Pt<sub>12</sub>(CO)<sub>24</sub>]<sup>2-</sup> with [Ni<sub>6</sub>(CO)<sub>12</sub>]<sup>2-</sup>, [Ni<sub>9</sub>(CO)<sub>18</sub>]<sup>2-</sup> and [H<sub>2</sub>Ni<sub>12</sub>(CO)<sub>21</sub>]<sup>2-</sup>, afforded [Pt<sub>9-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>18</sub>]<sup>2-</sup> (<i>x</i> = 0-9) species. [Pt<sub>6-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>12</sub>]<sup>2-</sup> (<i>x</i> = 1-5) were converted into [Pt<sub>12-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>21</sub>]<sup>4-</sup> (<i>x</i> = 2-10) upon heating in CH<sub>3</sub>CN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [Pt<sub>12-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>21</sub>]<sup>4-</sup> (<i>x</i> ≈ 8) with HBF<sub>4</sub>·Et<sub>2</sub>O afforded the [HPt<sub>14+<i>x</i></sub>Ni<sub>24-<i>x</i></sub>(CO)<sub>44</sub>]<sup>5-</sup> (<i>x</i> ≈ 0.7) nanocluster. Finally, [Pt<sub>19-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>22</sub>]<sup>4-</sup> (<i>x</i> = 2-6) could be obtained by heating [Pt<sub>9-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>18</sub>]<sup>2-</sup> (<i>x</i> = 1-3) in CH<sub>3</sub>CN at 80 °C, or [Pt<sub>6-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>12</sub>]<sup>2-</sup> (2-4) in DMSO at 130 °C. The molecular structures of these new alloy nanoclusters have been determined by single crystal X-ray diffraction. The site preference of Pt and Ni within their metal cages has been computationally investigated. The electrochemical and IR spectroelectrochemical behavior of [Pt<sub>19-<i>x</i></sub>Ni<sub><i>x</i></sub>(CO)<sub>22</sub>]<sup>4-</sup> (<i>x</i> = 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt<sub>19</sub>(CO)<sub>22</sub>]<sup>4-</sup>. Nanoclusters ; Alloy ; Crystallography ; Stoichiometry ; Materials science ; Metal ; Reagent ; Chemistry ; Metallurgy ; Physical chemistry ; Nanotechnology Nanocluster Synthesis and Applications ; Organometallic Complex Synthesis and Catalysis ; Inorganic Chemistry and Materials