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Thiopurine prodrugs are efficient UVA absorbers and singlet oxygen generators and the long\u2010term treatment with these prodrugs correlates with a high incidence of sunlight\u2010induced skin cancer in patients. In this contribution, we show that the electronic relaxation mechanisms and photochemical properties of azathioprine are remarkably different from those of 6\u2010mercaptopurine upon absorption of UVA radiation. UVA excitation of 6\u2010mercaptopurine results in nearly 100% triplet yield and up to 30% singlet oxygen generation, whereas excitation of azathioprine with UVA leads to triplet yields of 15\u20133% depending on pH of the aqueous solution and &lt;1% singlet oxygen generation. While photoexcitation of 6\u2010mercaptopurine and other thiopurine prodrugs can facilitate oxidatively generated cell damage, azathioprine's poor photosensitization ability reveals the use of interchromophoric charge\u2010transfer interactions for the molecular design of photostable prodrugs exhibiting a remarkable reduction in photocytotoxic side effects before drug metabolization.<\/jats:p>","DOI":"10.1111\/php.13513","type":"journal-article","created":{"date-parts":[[2021,9,4]],"date-time":"2021-09-04T10:07:08Z","timestamp":1630750028000},"page":"617-632","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Intramolecular Charge Transfer in the Azathioprine Prodrug Quenches Intersystem Crossing to the Reactive Triplet State in 6\u2010Mercaptopurine\n                    <sup>\u2020<\/sup>"],"prefix":"10.1111","volume":"98","author":[{"given":"Luis 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