The molecular [Pt33(CO)38]2- nanocluster was obtained from the thermal decomposition of Na2[Pt15(CO)30] in methanol. The reaction of [Pt19(CO)22]4- with acids (1-2 equiv) affords the unstable [Pt19(CO)22]3- trianion, which evolves with time leading eventually to the [Pt40(CO)40]6- hexa-Anion. The total structures of both nanoclusters were determined via single-crystal X-ray diffraction. [Pt33(CO)38]2- displays a defective ccp Pt33 core and shows that localized deformations occur in correspondence of atomic defects to "repair" them. In contrast, [Pt40(CO)40]6- shows a bcc Pt40 core and represents the largest Pt cluster with a body-centered structure. The rich electrochemistry of the two high-nuclearity platinum carbonyl clusters was studied by cyclic voltammetry and electrochemical in situ Fourier transform infrared spectroscopy. The redox changes of [Pt33(CO)38]2- show features of chemical reversibility and electrochemical quasi-reversibility, and the vibrational spectra in the CO stretching region of the nine redox forms of the cluster [Pt33(CO)38]n (n = 0 to â'4, â'6 to â'9) are reported. Almost all the redox processes exhibited by [Pt40(CO)40]6- are chemically and electrochemically reversible, and the eight oxidation states of [Pt40(CO)40] from â'4 to â'11 were spectroscopically characterized. The effect of the more regular bcc Pt-carbonyl cluster structure of [Pt40(CO)40]6- with respect to that of the defective ccp Pt33 core on the redox behavior is discussed.
Cattabriga, E., Ciabatti, I., Femoni, C., Funaioli, T., Iapalucci, M.C., Zacchini, S. (2016). Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38]2- and the bcc [Pt40(CO)40]6- Molecular Nanoclusters. INORGANIC CHEMISTRY, 55(12), 6068-6079 [10.1021/acs.inorgchem.6b00607].
Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38]2- and the bcc [Pt40(CO)40]6- Molecular Nanoclusters
CIABATTI, IACOPO;FEMONI, CRISTINA;IAPALUCCI, MARIA CARMELA;ZACCHINI, STEFANO
2016
Abstract
The molecular [Pt33(CO)38]2- nanocluster was obtained from the thermal decomposition of Na2[Pt15(CO)30] in methanol. The reaction of [Pt19(CO)22]4- with acids (1-2 equiv) affords the unstable [Pt19(CO)22]3- trianion, which evolves with time leading eventually to the [Pt40(CO)40]6- hexa-Anion. The total structures of both nanoclusters were determined via single-crystal X-ray diffraction. [Pt33(CO)38]2- displays a defective ccp Pt33 core and shows that localized deformations occur in correspondence of atomic defects to "repair" them. In contrast, [Pt40(CO)40]6- shows a bcc Pt40 core and represents the largest Pt cluster with a body-centered structure. The rich electrochemistry of the two high-nuclearity platinum carbonyl clusters was studied by cyclic voltammetry and electrochemical in situ Fourier transform infrared spectroscopy. The redox changes of [Pt33(CO)38]2- show features of chemical reversibility and electrochemical quasi-reversibility, and the vibrational spectra in the CO stretching region of the nine redox forms of the cluster [Pt33(CO)38]n (n = 0 to â'4, â'6 to â'9) are reported. Almost all the redox processes exhibited by [Pt40(CO)40]6- are chemically and electrochemically reversible, and the eight oxidation states of [Pt40(CO)40] from â'4 to â'11 were spectroscopically characterized. The effect of the more regular bcc Pt-carbonyl cluster structure of [Pt40(CO)40]6- with respect to that of the defective ccp Pt33 core on the redox behavior is discussed.File | Dimensione | Formato | |
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