Electron spin multiplicities of transition-metal aromatic radicals and ions: M[C6(CH3)6] and M+[(C 6(CH3)6] (M = Ti, V, and Co)

Jung Sup Lee, Yuxiu Lei, Dong Sheng Yang

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5 Scopus citations

Abstract

Determination of electron spin multiplicities of transition-metal radicals and ions challenges both experimentalists and theoreticians. In this work, we report preferred electron spin states of M[C6(CH3) 6] and M+(C6(CH3)6], where M = Ti, V, and Co. The neutral radicals were formed in a supersonic metal cluster beam source, and their masses were measured with time-of-flight mass spectrometry. Precise ionization energies of the radicals and metal-ligand stretching frequencies of the ions were measured by pulsed field ionization zero electron kinetic energy spectroscopy. C-H stretching frequencies of the methyl group in the radicals were obtained by infrared-ultraviolet two-photon ionization. Electron spin multiplicities of the radicals and ions were investigated by combining the spectroscopic measurements, density functional theory, and Franck-Condon factor calculations. The preferred spin states are quintet, sextet, and quartet for the neutral Ti, V, and Co radicals, respectively; for the corresponding singly charged cations, they are quartet, quintet, and triplet. In these high-spin states, the aromatic ring remains nearly planar. This finding contrasts to the previous study of Sc(hmbz), for which low-spin states are favored, and the aromatic ring is severely bent.

Original languageEnglish
Pages (from-to)6509-6517
Number of pages9
JournalJournal of Physical Chemistry A
Volume115
Issue number24
DOIs
StatePublished - Jun 23 2011

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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