Infrared spectroscopic and computational studies of Co(ClO4)2 dissolved in N,N-dimethylformamide (DMF). Vibrations of DMF influenced by Co2+ or ClO4 or both

Kazuhiko Ohashi, Hayato Takeshita

研究成果: Contribution to journalArticle査読

1 被引用数 (Scopus)

抄録

Infrared (IR) spectroscopy for N,N-dimethylformamide (DMF) shows that the OCN bend (δOCN) and the CO stretch (νCO) vibrations undergo an upshift and a downshift, respectively, on the dissolution of Co(ClO4)2. Quantum chemical calculations are performed for optimizing the structures and predicting the IR spectra of model complexes for solute species. The calculations reveal that Co2+ exerts a much larger influence than ClO4 on the vibrations of DMF. For Co2+(DMF)6, in which each DMF molecule is coordinated to Co2+ via the O atom, the Co2+⋯DMF interaction upshifts the δOCN frequencies (+24 cm−1 on average) while the dipole coupling gives rise to splitting (12 cm−1) of the modes. On the other hand, the Co2+⋯DMF interaction downshifts the νCO frequencies (−15 cm−1 on average) while the splitting of the modes amounts to 37 cm−1. As a result, one of the νCO modes is located at an upshifted position (+13 cm−1) despite the O-atom coordination. For six-coordinated isomers of Co2+(DMF)7, the δOCN and νCO frequencies of the second-sphere DMF are close to those of bulk DMF in neat liquid. The calculations indicate that it is difficult to prove or exclude the formation of contact ion pairs [Co(DMF)5ClO4]+ and solvent-shared ion pairs [Co(DMF)6ClO4]+ by IR spectroscopy in the δOCN and νCO regions. However, asymmetric ClO stretches of the ClO4 moiety suggest that conceivable is the coexistence of solvent-shared ion pairs only.

本文言語英語
論文番号119289
ジャーナルSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
248
DOI
出版ステータス出版済み - 3 5 2021

All Science Journal Classification (ASJC) codes

  • 分析化学
  • 原子分子物理学および光学
  • 器械工学
  • 分光学

フィンガープリント

「Infrared spectroscopic and computational studies of Co(ClO<sub>4</sub>)<sub>2</sub> dissolved in N,N-dimethylformamide (DMF). Vibrations of DMF influenced by Co<sup>2+</sup> or ClO<sub>4</sub><sup>−</sup> or both」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル