The reactions of ozone with ferrocene (cp(2)Fe) and with n-butylferrncene (n-butyl cp(2)Fe) were studied using matrix isolation, UV-vis spectroscopy, and theoretical calculations. The codeposition of cp(2)Fe with O-3 and of n-butyl cp(2)Fe with O-3 into an argon matrix led to the production of 1:1 charge-transfer complexes with absorptions at 765 and 815 nm, respectively. These absorptions contribute to the green matrix color observed upon initial deposition. The charge-transfer complexes underwent photochemical reactions upon irradiation with red light (lambda >= 600 nm). Theoretical UV-vis spectra of the charge-transfer complexes and photochemical products were calculated using TD-DFT at the B3LYP/6-311G++(d,2p) level of theory. The calculated UV-vis spectra were in good agreement with the experimental results. MO analysis of these long-wavelength transitions showed them to be n -> pi* on the ozone subunit in the complex and indicated that the formation of the charge-transfer complex between ozone and cp(2)Fe or n-butyl cp(2)Fe affects how readily the pi* orbital on O-3 is populated when red light (lambda >= 600 nm) is absorbed. 1:1 complexes of cp(2)Fe and n-butyl cp(2)Fe with O-2 were also observed experimentally and calculated theoretically. These results support and enhance previous infrared studies of the mechanism of photowddation of ferrocene by ozone, a reaction that has considerable significance for the formation of iron oxide thin films for a range of applications.