Thymine-2-14C was irradiated with UV light (>300 nm) in water solutions in the presence of different sensitizers. Pyrimidines upon irradiation with wavelengths of 300—320 nm in the presence of some ketones as sensitizers, yield cyclobutyl pyrimidine dimers. The reaction occurs through a triplet-triplet energy transfer from the sensitizer to the substrate. The energy transfer, however, does not occur through a simple physical mechanism. The ability of a donor (e. g. ketone molecule) in its excited state to form a complex with the acceptor (pyrimidine molecule) appears to be a prerequisite in this type of photodimerization reaction. A correlation of the photochemical behavior of different ketones in this reaction with the nature of their excited states has been proposed. Carbonyl compounds possessing n, π* lowest triples are active in inducing pyrimidine dimerizations. By introducing some different electron donating groups to the ketone molecules that lower its π, π* state below its n, π* level, the sensitizing ability of the molecule appears to decrease or disappears completely. Ethylacetoacetate was found to be a more effective sensitizer than acetone or acetophenone. Likewise, dihydroxyacetone was found to be a potent photosensitizer in dimerization of thymine. Urocanic acid (UCA), a major UV absorbing compound in mammalian skin, did not show any sensitizing ability to induce cyclobutyl pyrimidine dimers on irradiation in the presence of thymine, with wavelengths greater than 300 nm.
Manipulating spatial alignment of donor and acceptor in host-guest MOF for TADF