A multitechnique approach to spin-flips for Cp2Cr(II) chemistry in confined state

J. Estephane, E. Groppo*, J. G. Vitillo, A. Damin, D. Gianolio, C. Lamberti, S. Bordiga, E. A. Quadrelli, Jean-Marie Maurice Basset, G. Kervern, L. Emsley, G. Pintacuda, A. Zecchina

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations


Paramagnetic solid-state NMR, extended X-ray absorption fine structure (EXAFS), and Raman spectroscopies, along with detailed quantum mechanical calculations performed with different density functional theory (DFT) functionals, are successfully applied to investigate the magnetic, structural, and vibrational properties of molecularly isolated chromocene (Cp2Cr, where Cp = C5H5) and of its Cp2Cr(CO) adduct. Paramagnetic solid-state NMR unequivocally demonstrates that a spin flip occurs by coming from the paramagnetic Cp2Cr (triplet state) to the diamagnetic Cp2Cr(CO) adduct (singlet state), thus clarifying the theoretical dilemma of the disagreement among different functionals in predicting the most stable spin state. EXAFS and Raman spectroscopies are able to experimentally discriminate between singlet and triplet states, because a different spin state corresponds to a different geometry of the molecule, and therefore to different vibrational features. The here reported multitechnique approach could have great relevance in establishing the occurrence of spin flip in the chemical reactivity of transition metal complexes in both homo- and heterogeneous catalysis.

Original languageEnglish (US)
Pages (from-to)4451-4458
Number of pages8
JournalJournal of Physical Chemistry C
Issue number10
StatePublished - Mar 18 2010

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • General Energy
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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