Mass Spectrometric and Computational Studies of Heterofullerenes ([C 58Pt] -, [C 59Pt] +) Obtained by Laser Ablation of Electrochemically Deposited Films

Akari Hayashi, Yongming Xie, Josep M. Poblet, Josep M. Campanera, Carlito B Lebrilla, Alan L. Balch

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Fullerenes with metal atoms substituted into the carbon framework have been observed in laser ablation studies of electrochemically prepared C 60/Pt or C 60/Ir(CO) 2) films that contain polymeric, covalently bound chains: ⋯C 60ML xC 60ML xC 60ML x ⋯ (ML x = Ir(CO) 2 or Pt). The C 60/Pt film upon laser ablation produces the ions [C 58Pt] - and [C 56Pt] -, which result from the substitution of a platinum atom for two carbon atoms, and [C 57Pt 2] -, which incorporates two platinum atoms into the cage. The C 60/Ir(CO) 2 film produces a different series of products, [C 59Ir] -, [C 58Ir] -, [C 57Ir] -, and [C 56Ir] -, in which an iridium atom can replace one or two carbon atoms within the fullerene cage. Studies of the structures of [C 58M] - by density functional theory (DFT) show that the isomer with the metal atom replacing the C 2 unit at a 6:6 ring junction of the fullerene is more stable than the less symmetrical isomer with the metal replacing a C 2 unit at a 5:6 ring junction. Evidence for the ability of the metal atoms in some of these fullerenes to bind added ligands has been obtained by conducting the laser ablation studies in the presence of 2-butene, where adducts such as [C 29Ir(2-butene)] -, [C 58Ir(2-butene)] -, [C 57Ir(2-butene)] -, and [C 56Ir(2-butene)] - have been observed. DFT calculations were also carried out to analyze the reactivity of [C 58Pt] - and [C 58Ir] - with ethylene as a model for 2-butene. The formation energy of [C 58Ir(C 2H 4)] - from [C 58M] - and C 2H 4 was computed to be -15.8 kcal mol -1.

Original languageEnglish (US)
Pages (from-to)2192-2198
Number of pages7
JournalJournal of Physical Chemistry A
Volume108
Issue number12
DOIs
StatePublished - Mar 25 2004

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Laser ablation
laser ablation
butenes
Fullerenes
Atoms
fullerenes
atoms
Carbon Monoxide
Metals
Carbon
Platinum
Isomers
metals
Density functional theory
carbon
platinum
isomers
density functional theory
Iridium
rings

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Mass Spectrometric and Computational Studies of Heterofullerenes ([C 58Pt] -, [C 59Pt] +) Obtained by Laser Ablation of Electrochemically Deposited Films. / Hayashi, Akari; Xie, Yongming; Poblet, Josep M.; Campanera, Josep M.; Lebrilla, Carlito B; Balch, Alan L.

In: Journal of Physical Chemistry A, Vol. 108, No. 12, 25.03.2004, p. 2192-2198.

Research output: Contribution to journalArticle

Hayashi, Akari ; Xie, Yongming ; Poblet, Josep M. ; Campanera, Josep M. ; Lebrilla, Carlito B ; Balch, Alan L. / Mass Spectrometric and Computational Studies of Heterofullerenes ([C 58Pt] -, [C 59Pt] +) Obtained by Laser Ablation of Electrochemically Deposited Films. In: Journal of Physical Chemistry A. 2004 ; Vol. 108, No. 12. pp. 2192-2198.
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abstract = "Fullerenes with metal atoms substituted into the carbon framework have been observed in laser ablation studies of electrochemically prepared C 60/Pt or C 60/Ir(CO) 2) films that contain polymeric, covalently bound chains: ⋯C 60ML xC 60ML xC 60ML x ⋯ (ML x = Ir(CO) 2 or Pt). The C 60/Pt film upon laser ablation produces the ions [C 58Pt] - and [C 56Pt] -, which result from the substitution of a platinum atom for two carbon atoms, and [C 57Pt 2] -, which incorporates two platinum atoms into the cage. The C 60/Ir(CO) 2 film produces a different series of products, [C 59Ir] -, [C 58Ir] -, [C 57Ir] -, and [C 56Ir] -, in which an iridium atom can replace one or two carbon atoms within the fullerene cage. Studies of the structures of [C 58M] - by density functional theory (DFT) show that the isomer with the metal atom replacing the C 2 unit at a 6:6 ring junction of the fullerene is more stable than the less symmetrical isomer with the metal replacing a C 2 unit at a 5:6 ring junction. Evidence for the ability of the metal atoms in some of these fullerenes to bind added ligands has been obtained by conducting the laser ablation studies in the presence of 2-butene, where adducts such as [C 29Ir(2-butene)] -, [C 58Ir(2-butene)] -, [C 57Ir(2-butene)] -, and [C 56Ir(2-butene)] - have been observed. DFT calculations were also carried out to analyze the reactivity of [C 58Pt] - and [C 58Ir] - with ethylene as a model for 2-butene. The formation energy of [C 58Ir(C 2H 4)] - from [C 58M] - and C 2H 4 was computed to be -15.8 kcal mol -1.",
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T1 - Mass Spectrometric and Computational Studies of Heterofullerenes ([C 58Pt] -, [C 59Pt] +) Obtained by Laser Ablation of Electrochemically Deposited Films

AU - Hayashi, Akari

AU - Xie, Yongming

AU - Poblet, Josep M.

AU - Campanera, Josep M.

AU - Lebrilla, Carlito B

AU - Balch, Alan L.

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N2 - Fullerenes with metal atoms substituted into the carbon framework have been observed in laser ablation studies of electrochemically prepared C 60/Pt or C 60/Ir(CO) 2) films that contain polymeric, covalently bound chains: ⋯C 60ML xC 60ML xC 60ML x ⋯ (ML x = Ir(CO) 2 or Pt). The C 60/Pt film upon laser ablation produces the ions [C 58Pt] - and [C 56Pt] -, which result from the substitution of a platinum atom for two carbon atoms, and [C 57Pt 2] -, which incorporates two platinum atoms into the cage. The C 60/Ir(CO) 2 film produces a different series of products, [C 59Ir] -, [C 58Ir] -, [C 57Ir] -, and [C 56Ir] -, in which an iridium atom can replace one or two carbon atoms within the fullerene cage. Studies of the structures of [C 58M] - by density functional theory (DFT) show that the isomer with the metal atom replacing the C 2 unit at a 6:6 ring junction of the fullerene is more stable than the less symmetrical isomer with the metal replacing a C 2 unit at a 5:6 ring junction. Evidence for the ability of the metal atoms in some of these fullerenes to bind added ligands has been obtained by conducting the laser ablation studies in the presence of 2-butene, where adducts such as [C 29Ir(2-butene)] -, [C 58Ir(2-butene)] -, [C 57Ir(2-butene)] -, and [C 56Ir(2-butene)] - have been observed. DFT calculations were also carried out to analyze the reactivity of [C 58Pt] - and [C 58Ir] - with ethylene as a model for 2-butene. The formation energy of [C 58Ir(C 2H 4)] - from [C 58M] - and C 2H 4 was computed to be -15.8 kcal mol -1.

AB - Fullerenes with metal atoms substituted into the carbon framework have been observed in laser ablation studies of electrochemically prepared C 60/Pt or C 60/Ir(CO) 2) films that contain polymeric, covalently bound chains: ⋯C 60ML xC 60ML xC 60ML x ⋯ (ML x = Ir(CO) 2 or Pt). The C 60/Pt film upon laser ablation produces the ions [C 58Pt] - and [C 56Pt] -, which result from the substitution of a platinum atom for two carbon atoms, and [C 57Pt 2] -, which incorporates two platinum atoms into the cage. The C 60/Ir(CO) 2 film produces a different series of products, [C 59Ir] -, [C 58Ir] -, [C 57Ir] -, and [C 56Ir] -, in which an iridium atom can replace one or two carbon atoms within the fullerene cage. Studies of the structures of [C 58M] - by density functional theory (DFT) show that the isomer with the metal atom replacing the C 2 unit at a 6:6 ring junction of the fullerene is more stable than the less symmetrical isomer with the metal replacing a C 2 unit at a 5:6 ring junction. Evidence for the ability of the metal atoms in some of these fullerenes to bind added ligands has been obtained by conducting the laser ablation studies in the presence of 2-butene, where adducts such as [C 29Ir(2-butene)] -, [C 58Ir(2-butene)] -, [C 57Ir(2-butene)] -, and [C 56Ir(2-butene)] - have been observed. DFT calculations were also carried out to analyze the reactivity of [C 58Pt] - and [C 58Ir] - with ethylene as a model for 2-butene. The formation energy of [C 58Ir(C 2H 4)] - from [C 58M] - and C 2H 4 was computed to be -15.8 kcal mol -1.

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