Direct Reactions from Excited States of the Drug

6 DIRECT REACTIONS FROM EXCITED STATES OF THE DRUG 

The substances for which this phenomenon has been observed are invariably polycyclic aromatic hydrocarbon structures. No exciplex formation has been reported in the literature to involve drug molecules, but this remains a possibility in concentrated solution or perhaps in solid-state mixtures. The consequences of exciplex formation are a radiative or nonradiative return to the ground state without chemical change, or electron transfer leading to chemical reaction of the drug, the quencher, or both. Many photoaddition processes are postulated to proceed via exciplex formation with the quencher molecule becoming chemically bound. 

The electronically excited state of a molecule will act as a more powerful electron donor or acceptor than the ground state. The reactions that can occur are, respectively, oxidative or reductive quenching  

The exact nature of the reaction (oxidative vs. reductive) will depend on the redox properties of I ) and Q. The electron transfer process is a special case of exciplex formation favored in the strongly polar solvents, such as water. The involvement of an exciplex in a photochemical reaction is generally established by studying the effects of known exciplex quenchers such as amines on the exciplex fluorescence and the product formation. The heavy atom effect, due to the presence of substituents such as bromine or iodine intra- or intermolecularly, causes an exciplex to move to the triplet state preferentially, with a quenching of fluorescence. 

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