Strong interfullerene electronic communication in a bisfullerene- hexarhodium sandwich complex

Kwangyeol Lee, Yoon Jeong Choi, Youn Jaung Cho, Chang Yeon Lee, Hyunjoon Song, Chang Hoon Lee, Yoon Sup Lee, Joon T. Park

Research output: Contribution to journalArticle

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Abstract

Reaction of Rh6(CO)12(dppm)2 (dppm = 1,2-bis(diphenylphosphino)methane) with 1.4 equiv. of C60 in chlorobenzene at 120 °C affords a face-capping C60 derivative Rh6(CO)9(dppm)23- η222-C60) (1) in 73% yield. Treatment of 1 with excess CNR (10 equiv., R = CH2C 6H5) at 80 °C provides a bisbenzylisocyanide- substituted compound Rh6(CO)7(dppm)2(CNR) 2322, η2-C60) (2) in 59% yield. Reaction of 1 with excess C60 (4 equiv.) in refluxing chlorobenzene followed by treatment with 1 equiv. of CNR at room temperature gives a bisfullerene sandwich complex Rh6(CO)5(dppm)2(CNR)(μ3- η222-C60) 2 (3) in 31% yield. Compounds 1, 2, and 3 have been characterized by spectroscopic and microanalytical methods as well as by X-ray crystallographic studies. Electrochemical properties of 1, 2, and 3 have been examined by cyclic voltammetry. The cyclic voltammograms (CVs) of 1 and 2 show two reversible one-electron redox waves, a reversible one-step two-electron redox wave, and a reversible one-electron redox wave, respectively, within the solvent cutoff window. This observation suggests that compounds 1 and 2 undergo similar C 60-localized electrochemical pathways up to 15 and 2 5-. Each redox wave of 2 appears at more negative potentials compared to that of 1 because of the donor effect of the benzylisocyanide ligand. The CV of compound 3 reveals six reversible well-separated redox waves due to strong interfullerene electronic communication via the Rh6 metal cluster bridge. The electrochemical properties of 1, 2, and 3 have been rationalized by molecular orbital calculations using the density functional theory (DFT) method. In particular, the molecular orbital (MO) calculation reveals significant contribution of the metal cluster center to the unoccupied molecular orbitals in 3, which is consistent with the experimental result of strong interfullerene electronic communication via the Rh6 metal cluster spacer.

Original languageEnglish
Pages (from-to)9837-9844
Number of pages8
JournalJournal of the American Chemical Society
Volume126
Issue number31
DOIs
Publication statusPublished - 2004 Aug 11

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Oxidation-Reduction
Molecular orbitals
Communication
Orbital calculations
Metals
Electrons
Electrochemical properties
Methane
Cyclic voltammetry
Density functional theory
Ligands
X-Rays
Derivatives
X rays
Temperature
chlorobenzene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Strong interfullerene electronic communication in a bisfullerene- hexarhodium sandwich complex. / Lee, Kwangyeol; Choi, Yoon Jeong; Cho, Youn Jaung; Lee, Chang Yeon; Song, Hyunjoon; Lee, Chang Hoon; Lee, Yoon Sup; Park, Joon T.

In: Journal of the American Chemical Society, Vol. 126, No. 31, 11.08.2004, p. 9837-9844.

Research output: Contribution to journalArticle

Lee, Kwangyeol ; Choi, Yoon Jeong ; Cho, Youn Jaung ; Lee, Chang Yeon ; Song, Hyunjoon ; Lee, Chang Hoon ; Lee, Yoon Sup ; Park, Joon T. / Strong interfullerene electronic communication in a bisfullerene- hexarhodium sandwich complex. In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 31. pp. 9837-9844.
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abstract = "Reaction of Rh6(CO)12(dppm)2 (dppm = 1,2-bis(diphenylphosphino)methane) with 1.4 equiv. of C60 in chlorobenzene at 120 °C affords a face-capping C60 derivative Rh6(CO)9(dppm)2(μ3- η2,η2,η2-C60) (1) in 73{\%} yield. Treatment of 1 with excess CNR (10 equiv., R = CH2C 6H5) at 80 °C provides a bisbenzylisocyanide- substituted compound Rh6(CO)7(dppm)2(CNR) 2(μ3-η2,η2, η2-C60) (2) in 59{\%} yield. Reaction of 1 with excess C60 (4 equiv.) in refluxing chlorobenzene followed by treatment with 1 equiv. of CNR at room temperature gives a bisfullerene sandwich complex Rh6(CO)5(dppm)2(CNR)(μ3- η2,η2,η2-C60) 2 (3) in 31{\%} yield. Compounds 1, 2, and 3 have been characterized by spectroscopic and microanalytical methods as well as by X-ray crystallographic studies. Electrochemical properties of 1, 2, and 3 have been examined by cyclic voltammetry. The cyclic voltammograms (CVs) of 1 and 2 show two reversible one-electron redox waves, a reversible one-step two-electron redox wave, and a reversible one-electron redox wave, respectively, within the solvent cutoff window. This observation suggests that compounds 1 and 2 undergo similar C 60-localized electrochemical pathways up to 15 and 2 5-. Each redox wave of 2 appears at more negative potentials compared to that of 1 because of the donor effect of the benzylisocyanide ligand. The CV of compound 3 reveals six reversible well-separated redox waves due to strong interfullerene electronic communication via the Rh6 metal cluster bridge. The electrochemical properties of 1, 2, and 3 have been rationalized by molecular orbital calculations using the density functional theory (DFT) method. In particular, the molecular orbital (MO) calculation reveals significant contribution of the metal cluster center to the unoccupied molecular orbitals in 3, which is consistent with the experimental result of strong interfullerene electronic communication via the Rh6 metal cluster spacer.",
author = "Kwangyeol Lee and Choi, {Yoon Jeong} and Cho, {Youn Jaung} and Lee, {Chang Yeon} and Hyunjoon Song and Lee, {Chang Hoon} and Lee, {Yoon Sup} and Park, {Joon T.}",
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AU - Choi, Yoon Jeong

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AU - Lee, Chang Yeon

AU - Song, Hyunjoon

AU - Lee, Chang Hoon

AU - Lee, Yoon Sup

AU - Park, Joon T.

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N2 - Reaction of Rh6(CO)12(dppm)2 (dppm = 1,2-bis(diphenylphosphino)methane) with 1.4 equiv. of C60 in chlorobenzene at 120 °C affords a face-capping C60 derivative Rh6(CO)9(dppm)2(μ3- η2,η2,η2-C60) (1) in 73% yield. Treatment of 1 with excess CNR (10 equiv., R = CH2C 6H5) at 80 °C provides a bisbenzylisocyanide- substituted compound Rh6(CO)7(dppm)2(CNR) 2(μ3-η2,η2, η2-C60) (2) in 59% yield. Reaction of 1 with excess C60 (4 equiv.) in refluxing chlorobenzene followed by treatment with 1 equiv. of CNR at room temperature gives a bisfullerene sandwich complex Rh6(CO)5(dppm)2(CNR)(μ3- η2,η2,η2-C60) 2 (3) in 31% yield. Compounds 1, 2, and 3 have been characterized by spectroscopic and microanalytical methods as well as by X-ray crystallographic studies. Electrochemical properties of 1, 2, and 3 have been examined by cyclic voltammetry. The cyclic voltammograms (CVs) of 1 and 2 show two reversible one-electron redox waves, a reversible one-step two-electron redox wave, and a reversible one-electron redox wave, respectively, within the solvent cutoff window. This observation suggests that compounds 1 and 2 undergo similar C 60-localized electrochemical pathways up to 15 and 2 5-. Each redox wave of 2 appears at more negative potentials compared to that of 1 because of the donor effect of the benzylisocyanide ligand. The CV of compound 3 reveals six reversible well-separated redox waves due to strong interfullerene electronic communication via the Rh6 metal cluster bridge. The electrochemical properties of 1, 2, and 3 have been rationalized by molecular orbital calculations using the density functional theory (DFT) method. In particular, the molecular orbital (MO) calculation reveals significant contribution of the metal cluster center to the unoccupied molecular orbitals in 3, which is consistent with the experimental result of strong interfullerene electronic communication via the Rh6 metal cluster spacer.

AB - Reaction of Rh6(CO)12(dppm)2 (dppm = 1,2-bis(diphenylphosphino)methane) with 1.4 equiv. of C60 in chlorobenzene at 120 °C affords a face-capping C60 derivative Rh6(CO)9(dppm)2(μ3- η2,η2,η2-C60) (1) in 73% yield. Treatment of 1 with excess CNR (10 equiv., R = CH2C 6H5) at 80 °C provides a bisbenzylisocyanide- substituted compound Rh6(CO)7(dppm)2(CNR) 2(μ3-η2,η2, η2-C60) (2) in 59% yield. Reaction of 1 with excess C60 (4 equiv.) in refluxing chlorobenzene followed by treatment with 1 equiv. of CNR at room temperature gives a bisfullerene sandwich complex Rh6(CO)5(dppm)2(CNR)(μ3- η2,η2,η2-C60) 2 (3) in 31% yield. Compounds 1, 2, and 3 have been characterized by spectroscopic and microanalytical methods as well as by X-ray crystallographic studies. Electrochemical properties of 1, 2, and 3 have been examined by cyclic voltammetry. The cyclic voltammograms (CVs) of 1 and 2 show two reversible one-electron redox waves, a reversible one-step two-electron redox wave, and a reversible one-electron redox wave, respectively, within the solvent cutoff window. This observation suggests that compounds 1 and 2 undergo similar C 60-localized electrochemical pathways up to 15 and 2 5-. Each redox wave of 2 appears at more negative potentials compared to that of 1 because of the donor effect of the benzylisocyanide ligand. The CV of compound 3 reveals six reversible well-separated redox waves due to strong interfullerene electronic communication via the Rh6 metal cluster bridge. The electrochemical properties of 1, 2, and 3 have been rationalized by molecular orbital calculations using the density functional theory (DFT) method. In particular, the molecular orbital (MO) calculation reveals significant contribution of the metal cluster center to the unoccupied molecular orbitals in 3, which is consistent with the experimental result of strong interfullerene electronic communication via the Rh6 metal cluster spacer.

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