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Creators/Authors contains: "Boldissar, Samuel"

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  1. ; ; ; ; ; (, Photochemistry and Photobiology)
    Abstract 2,6‐Diaminopurine (2,6‐dAP) is an alternative nucleobase that potentially played a role in prebiotic chemistry. We studied its excited state dynamics in the gas phase by REMPI, IR‐UV hole burning, and ps pump‐probe spectroscopy and performed quantum chemical calculations at the SCS‐ADC(2) level of theory to interpret the experimental results. We found the 9H tautomer to have a small barrier to ultrafast relaxation via puckering of its 6‐membered ring. The 7H tautomer has a larger barrier to reach a conical intersection and also has a sizable triplet yield. These results are discussed relative to other purines, for which 9H tautomerization appears to be more photostable than 7H and homosubstituted purines appear to be less photostable than heterosubstituted or singly substituted purines. 
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