The ozonolsis of ferrocene (Fc) and of n-butylferrocene (nBuFc) was studied using matrix isolation, UV-Vis spectroscopy, and theoretical calculations. The co-deposition of Fc with ozone (O3) and that of n-BuFc with O3 led to production of green charge transfer complexes (Fc-O3 and nBuFc-O3 respectively). These charge transfer complexes underwent photochemical reactions upon irradiation with red light (λ ≥ 600 nm). This work expands upon the results of matrix isolation studies that previously characterized the photochemical products by FT-IR spectroscopy. Theoretical UV-Vis spectra of proposed charge transfer complexes and photochemical products were calculated with DFT using a TD-B3LYP functional and the 6-311G++(d,2p) basis set. The experimental UV-Vis spectra each showed a long wavelength broad band, at 750 nm for Fc/O3 and at 760 nm for nBuFc/O3. These absorptions contribute to the green matrix color observed prior to irradiation. After red irradiation these bands decreased significantly and new bands formed as a result of the photochemical reaction. The calculated UV-Vis spectra for both the proposed charged transfer species and the photochemical products are in excellent agreement with the experimental results. Furthermore, the UV-Vis spectra calculations for the proposed charge transfer complexes provided information about the molecular orbitals (MO) involved in the absorptions corresponding to the green matrix color. The MO analysis of the long wavelength transitions indicated a shift in electron density from Fc or nBuFc to O3 as these transitions occur.

Charge transfer complexes and photochemistry of ozone with n-butylferrocene and ferrocene: A UV-Vis matrix isolation study

249th National Meeting (2015)

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