| Abstract: | We report on the experimental and theoretical studies of the flexible organometallic complex Cp2Mo(dmit) which often exhibits a folding in the solid state. Raman spectra of charge‐transfer salts formed by Cp2Mo(dmit) with various anions (Br−, BF4−, PF6−, SbF6−, ReO(dmit)2−, TCNQF4−) were measured at room temperature using red (632.8 nm) and near‐infrared (780 nm) excitations. The influence of the folding of the MoS2C2 metallacycle in Cp2Mo(dmit)]+• cation on the Raman spectra was investigated. Due to folding of Cp2Mo(dmit)]+•, the bands related to the CC and some C S stretching vibrations shift toward lower wavenumbers by about 0.5–0.6 cm−1deg−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. |
