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Flexibility of paramagnetic (d 1 ) organometallic dithiolene complex [Cp 2 Mo(dmit)] +• studied by Raman spectroscopy
Author(s) -
Świetlik Roman,
Łapiński Andrzej,
Fourmigué Marc,
Yakushi Kyuya
Publication year - 2009
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.2377
Subject(s) - raman spectroscopy , chemistry , homo/lumo , density functional theory , molecular orbital , crystallography , spectral line , analytical chemistry (journal) , computational chemistry , molecule , physics , organic chemistry , chromatography , optics , astronomy
We report on the experimental and theoretical studies of the flexible organometallic complex Cp 2 Mo(dmit) which often exhibits a folding in the solid state. Raman spectra of charge‐transfer salts formed by Cp 2 Mo(dmit) with various anions (Br − , BF 4 − , PF 6 − , SbF 6 − , ReO(dmit) 2 − , TCNQF 4 − ) were measured at room temperature using red (632.8 nm) and near‐infrared (780 nm) excitations. The influence of the folding of the MoS 2 C 2 metallacycle in [Cp 2 Mo(dmit)] +• cation on the Raman spectra was investigated. Due to folding of [Cp 2 Mo(dmit)] +• , the bands related to the CC and some CS stretching vibrations shift toward lower wavenumbers by about 0.5–0.6 cm −1 deg −1 . The bond lengths, charge distribution on atoms, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies, and dipole moments for neutral and ionized complex with various folding angles were calculated by density functional theory (DFT) methods. Additionally, the normal vibrational modes and theoretical Raman spectra were calculated and compared with experimental data. Our results indicate that vibrational spectroscopy can be applied for investigation of complex deformations in the solid state. Copyright © 2009 John Wiley & Sons, Ltd.