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.

Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38]2- and the bcc [Pt40(CO)40]6- Molecular Nanoclusters / Cattabriga, Enrico; Ciabatti, Iacopo; Femoni, Cristina; Funaioli, Tiziana; Iapalucci, Maria Carmela; Zacchini, Stefano. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 55:12(2016), pp. 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.
2016
Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38]2- and the bcc [Pt40(CO)40]6- Molecular Nanoclusters / Cattabriga, Enrico; Ciabatti, Iacopo; Femoni, Cristina; Funaioli, Tiziana; Iapalucci, Maria Carmela; Zacchini, Stefano. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 55:12(2016), pp. 6068-6079. [10.1021/acs.inorgchem.6b00607]
Cattabriga, Enrico; Ciabatti, Iacopo; Femoni, Cristina; Funaioli, Tiziana; Iapalucci, Maria Carmela; Zacchini, Stefano
File in questo prodotto:
File Dimensione Formato  
InorgChem2016PostPrint.pdf

accesso aperto

Tipo: Postprint
Licenza: Licenza per accesso libero gratuito
Dimensione 3.2 MB
Formato Adobe PDF
3.2 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/571025
Citazioni
  • ???jsp.display-item.citation.pmc??? 4
  • Scopus 33
  • ???jsp.display-item.citation.isi??? 31
social impact