Photochemistry and photophysics of anthracenes on silica gel
thesisposted on 12.11.2015 by Sian L. Williams
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Studies have been carried out investigating the photochemical and photophysical properties of anthracene adsorbed on silica gel. The photochemistry and photo physics of anthracene in solution are well reported and known, hence its choice as a probe for the silica gel surface. UV -visible absorption and fluorescence spectra of anthracene adsorbed on silica gel reveal aggregate formation at very low loadings (1 % of a monolayer) indicating preferential adsorption occurs at some surface sites. Laser flash photolysis at 355 nm produces both the triplet and radical cation of anthracene, their production was found to be mono- and multi-photonic respectively. The decays of both these transients were complex and the rates increased with increasing loading. Analysis of the triplet state decay has been carried out by studying the delayed fluorescence which arises from triplet triplet annihilation. Fractal and twodimensional models have been used to describe this bimolecular decay. The coadsorption of anthracene and an electron donor having an oxidation potential below 1.09 V on silica gel causes electron transfer to occur from the electron donor to the anthracene radical cation produced following laser flash photolysis at 355 nm. Studies using a selection of electron donors with varying reduction potentials were carried out. The electron donor transfers an electron to the anthracene radical cation, thus greatly accelerating its rate of decay; for electron donors such as triphenylamine, N,N-dimethylaniline and N,N,N',N'tetramethyl- l,4-phenylenediamine the rise of the donor radical cation is observed as the anthracene cation decays. These systems were studied using fluorescence measurements and laser flash photolysis to study any fluorescence quenching and the rate of decay of both the anthracene triplet and radical cation. A selection of anthracene derivatives adsorbed onto silica gel were also briefly studied to see the effect of substituent group and its position. Symmetrically substituted dialkoxyanthracenes and 9-cyanoanthracene were used. The transient absorption spectra of the 2,3- and 2,6-dialkoxyderivatives and 9-cyanoanthracene revealed spectral similarities with that of unsubstituted anthracene. The spectra of9,10- and I,S-didecyloxyanthracene showed significant differences in the radical cation spectra to those obtained for unsubstituted anthracene.