Charge-transfer spectra of ferrocene in halocarbon solvents under photoexcitation

Abstract

The changes in the electronic absorption spectra of ferrocene in the halocarbon solvents chloroform and carbontetrachloride have been investigated under photoexcitation in nitrogen atmosphere. Photoexcitations have been made with monochromatic light (using an Xe-source and a monochromator), at intervals of a few nanometers in the spectral range 220-750 nm. Analysing the spectra by a modified method the position of the charge-transfer-to-solvent (CTTS) band has been located for both the solvents. The position of the CTTS band in the case of carbontetrachloride solution located (320 nm) by the present study is different from the previously reported value (307 nm), while from the previous studies the position of the CTTS band in the case of the spectra of ferrocene in chloroform was not clear. From the present investigation, the changes in spectra after photoexcitation studied as a function, the concentration of ferrocene in the solution and the time (duration) of photoexcitations, have been observed to be systematic. Using the position of the new band (320 nm) for the CTTS transition in the case of carbontetrachloride, ionization potential of ferrocene has been estimated and the estimated value has shown excellent agreement with the experimental value indicating the exactness of the newly located CTTS band position.

Experimental and computational studies of novel ferrocene–pyranylidene dyads: Synthesis, characterization and electrochemical and linear optical properties

“…The shape of the UV–visible absorption spectrum of the new synthesized dyads in chloroform is different from that in other solvents. In polyhalogenated solvents such as chloroform, formation of charge transfer complexes of ferrocene with solvent occurs, this ferrocene to solvent charge transfer phenomenon having been predicted in previous studies …”

Synthesis, structural characterization, modal membrane interaction and anti-tumor cell line studies of nitrophenyl ferrocenes

“…When these compounds were probed in the SDS negative membrane a new band at about 650 -715 nm was appeared, This new band may be assigned to the oxidation of ferrocene to ferrocenium specie in accordance with literature[37].…”

Macromolecules Containing Redox-Active Neutral and Cationic Iron Complexes

“…Ferrocene-based polymeric systems are some of the most well-studied organometallic macromolecules, and their electrochemical properties have also been studied extensively. 2c, It has been shown by Manners and co-workers that communication between iron centers in polymers is dependent on the nature of the organic/inorganic bridging groups 1e. Recently, it was shown that silicon-bridged [1]ferrocenophanes undergo photolytic living ring-opening polymerization in the presence of nucleophilic anionic initiators . It was proposed that the ring-opening of the [1]ferrocenophanes was facilitated via photoinduced MLCT transitions, which further weakened the already weak Fe−Cp bonds, thus allowing for nucleophilic attack at the iron centers 7a.…”

“…Recently, it was shown that silicon-bridged [1]ferrocenophanes undergo photolytic living ring-opening polymerization in the presence of nucleophilic anionic initiators . It was proposed that the ring-opening of the [1]ferrocenophanes was facilitated via photoinduced MLCT transitions, which further weakened the already weak Fe−Cp bonds, thus allowing for nucleophilic attack at the iron centers 7a. The resulting poly(ferrocenylsilanes) were not photoactive since the HOMO−LUMO transition for these polymers was similar to that of ferrocene and exhibit no significant MLCT character.…”