Raman Spectra of Persistent Radical Anions from Benzophenone, Fluorenone, 2,2′-Bipyridyl, 4,4′-Di-tert-butyl-2,2′-dipyridyl, and Anthracene: Excellent Agreement between DFT and Experiment for Highly Delocalized Radical Systems

We report detailed Rainan spectra for the neutral and radical anion forms of benzophenone, fluorenone, 2,2'-bipyridyl, 4,4'-di-tert-butyl-2,2'-dipyridyl, and anthracene. Density functional theory (DFT) predictions for the Raman spectra of these molecules give additional insight into the assignment of each vibrational mode. While the use of DFT has been problematic in quantifying the thermochemistry of highly delocalized radicals, we find that DFT-predicted spectra using the popular B3LYP functional are in excellent agreement with the observed Raman spectra. In the case of the two bipyridyl compounds, the Raman spectra allowed us to conclude that the cis form of the radical anion complexed to a sodium cation was the preferred configuration. Benzophenone and fluorenone radical anions gave a significantly weakened C=O bond stretching vibrational frequency as expected from the population of an antibonding pi* orbital. For benzophenone, the C=O vibration dropped from 1659 to 1403 cm(-1) upon reduction. Similarly, fluorenone showed a C=O vibration observed at 1719 cm(-1) for the neutral form that decreased to 1522 cm(-1) for the radical anion. The structurally rigid anthracene showed relatively smaller Raman band shifts upon single-electron reduction as the pi* orbital is more equally delocalized on the entire structure. In total, we correlated 65 DFT-predicted vibrational modes for the neutral molecules with an overall error of 7.1 cm(-1) (root-mean-square errors (RMSEs)) and 67 DFT-predicted vibrational modes for radical anions with an overall error of 9.9 cm(-1). These comparisons between theory and experiment are another example to demonstrate the power of DFT in predicting the identity and geometry of molecules using Raman spectroscopy.

Automated summary

This study presents detailed Raman spectra for various molecules in neutral and radical anion forms, with DFT predictions showing good agreement with experimental results. The use of DFT in quantifying highly delocalized radicals remains problematic, but the B3LYP functional performs well in predicting Raman spectra. The comparisons between theory and experiment demonstrate the power of DFT in predicting molecular identity and geometry using Raman spectroscopy.