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Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
Published on: October 18, 2018
Examination of the charge-sensitive vibrational modes in bis(ethylenedithio)tetrathiafulvalene
Takashi Yamamoto1, Mikio Uruichi, Kaoru Yamamoto
1Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan. yamataka@ims.ac.jp
Abstract:
We reinvestigated the two C=C stretching modes of the five-membered rings of ET (ET = bis(ethylenedithio)tetrathiafulvalene), namely, nu(2) (in-phase mode) and nu(27) (out-of-phase mode). The frequency of the nu(27) mode of ET(+) was corrected to be approximately 1400 cm(-1), which was identified from the polarized infrared reflectance spectra of (ET)(ClO(4)), (ET)(AuBr(2)Cl(2)), and the deuterium- or (13)C-substituted compounds of (ET)(AuBr(2)Cl(2)). It was clarified from DFT calculations that the frequency of the nu(27) mode of the flat ET(0) molecule was significantly different from that of the boat-shaped ET(0) molecule. We obtained the linear relationship between the frequency and the charge on the molecule, rho, for the flat ET molecule, which was shown to be nu(27)(rho) = 1398 + 140(1 - rho) cm(-1). The frequency shift due to oxidation is remarkably larger than that reported in previous studies. The fractional charges of several ET salts in a charge-ordered state can be successfully estimated by applying this relationship. Therefore, the nu(27) mode is an efficient probe to detect rho in the charge-transfer salts of ET. Similarly, a linear relationship for the nu(2) mode was obtained as nu(2)(rho) = 1447 + 120(1 - rho). This relationship was successfully applied to the charge-poor molecule of theta-type ET salts in the charge-ordered state but could not be applied to the charge-rich molecule. This discrepancy was semiquantitatively explained by the hybridization between the nu(2) and nu(3) modes.
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