Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO)5 and Its Parent Compound Mn2(CO)10

Hana Cho, Kiryong Hong, Matthew L. Strader, Jae Hyuk Lee, Robert W. Schoenlein, Nils Huse, Tae Kyu Kim

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

We present a time-resolved X-ray spectroscopic study of the structural and electronic rearrangements of the photocatalyst Mn2(CO)10 upon photocleavage of the metal-metal bond. Our study of the manganese K-edge fine structure reveals details of both the molecular structure and valence charge distribution of the photodissociated radical product. Transient X-ray absorption spectra of the formation of the Mn(CO)5 radical demonstrate surprisingly small structural modifications between the parent molecule and the resulting two identical manganese monomers. Small modifications of the local valence charge distribution are decisive for the catalytic activity of the radical product. The spectral changes reflect altered hybridization of metal-3d, metal-4p, and ligand-2p orbitals, particularly loss of interligand interaction, accompanied by the necessary spin transition due to radical formation. The spectral changes in the manganese pre- and main-edge region are well-reproduced by time-dependent density functional theory and ab initio multiple scattering calculations.

Original languageEnglish
Pages (from-to)5895-5903
Number of pages9
JournalInorganic Chemistry
Volume55
Issue number12
DOIs
Publication statusPublished - 2016 Jun 20

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Photocatalysts
Molecular structure
Electronic structure
molecular structure
Manganese
Metals
electronic structure
manganese
Charge distribution
metals
charge distribution
valence
Multiple scattering
X ray absorption
products
Density functional theory
catalytic activity
Absorption spectra
Catalyst activity
x rays

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Cho, Hana ; Hong, Kiryong ; Strader, Matthew L. ; Lee, Jae Hyuk ; Schoenlein, Robert W. ; Huse, Nils ; Kim, Tae Kyu. / Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO)5 and Its Parent Compound Mn2(CO)10. In: Inorganic Chemistry. 2016 ; Vol. 55, No. 12. pp. 5895-5903.
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Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO)5 and Its Parent Compound Mn2(CO)10. / Cho, Hana; Hong, Kiryong; Strader, Matthew L.; Lee, Jae Hyuk; Schoenlein, Robert W.; Huse, Nils; Kim, Tae Kyu.

In: Inorganic Chemistry, Vol. 55, No. 12, 20.06.2016, p. 5895-5903.

Research output: Contribution to journalArticle

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AU - Cho, Hana

AU - Hong, Kiryong

AU - Strader, Matthew L.

AU - Lee, Jae Hyuk

AU - Schoenlein, Robert W.

AU - Huse, Nils

AU - Kim, Tae Kyu

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N2 - We present a time-resolved X-ray spectroscopic study of the structural and electronic rearrangements of the photocatalyst Mn2(CO)10 upon photocleavage of the metal-metal bond. Our study of the manganese K-edge fine structure reveals details of both the molecular structure and valence charge distribution of the photodissociated radical product. Transient X-ray absorption spectra of the formation of the Mn(CO)5 radical demonstrate surprisingly small structural modifications between the parent molecule and the resulting two identical manganese monomers. Small modifications of the local valence charge distribution are decisive for the catalytic activity of the radical product. The spectral changes reflect altered hybridization of metal-3d, metal-4p, and ligand-2p orbitals, particularly loss of interligand interaction, accompanied by the necessary spin transition due to radical formation. The spectral changes in the manganese pre- and main-edge region are well-reproduced by time-dependent density functional theory and ab initio multiple scattering calculations.

AB - We present a time-resolved X-ray spectroscopic study of the structural and electronic rearrangements of the photocatalyst Mn2(CO)10 upon photocleavage of the metal-metal bond. Our study of the manganese K-edge fine structure reveals details of both the molecular structure and valence charge distribution of the photodissociated radical product. Transient X-ray absorption spectra of the formation of the Mn(CO)5 radical demonstrate surprisingly small structural modifications between the parent molecule and the resulting two identical manganese monomers. Small modifications of the local valence charge distribution are decisive for the catalytic activity of the radical product. The spectral changes reflect altered hybridization of metal-3d, metal-4p, and ligand-2p orbitals, particularly loss of interligand interaction, accompanied by the necessary spin transition due to radical formation. The spectral changes in the manganese pre- and main-edge region are well-reproduced by time-dependent density functional theory and ab initio multiple scattering calculations.

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