Effect of substituents on the excited-state dynamics of the modified DNA bases 2,4-diaminopyrimidine and 2,6-diaminopurine

Literature Information

Publication Date 2010-04-08
DOI 10.1039/B917852J
Impact Factor 3.676
Authors

Zsolt Gengeliczki, Michael P. Callahan, Nathan Svadlenak, Csaba István Pongor, Leo Meerts, Dana Nachtigallová, Pavel Hobza, Mario Barbatti, Mattanjah S. de Vries


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Abstract

To explore the excited state dynamics of pyrimidine derivatives, we performed a combined experimental and theoretical study. We present resonant two-photon ionization (R2PI) and IR-UV double resonance spectra of 2,4-diaminopyrimidine and 2,6-diaminopurine seeded in a supersonic jet by laser desorption. For 2,4-diaminopyrimidine (S0 → S1 34 459 cm−1), we observed only the diamino tautomer with an excited state lifetime bracketed between experimental limits of 10 ps and 1 ns. For 2,6-diaminopurine, we observed two tautomers, the 9H- (S0 → S1 34 881 cm−1) and 7H- (S0 → S1 32 215 cm−1) diamino forms, with excited state lifetimes of 6.3 ± 0.4 ns and 8.7 ± 0.8 ns, respectively. We investigated the nature of the excited state of 2,4-diaminopyrimidine by means of multi-reference ab initio methods. The calculations of stationary points in the ground and excited states, minima on the S0/S1 crossing seam and connecting reaction paths show that several paths with negligible barriers exist, allowing ultrafast radiationless deactivation if excited at energies slightly higher than the band origin. The sub-nanosecond lifetime found experimentally is in good agreement with this finding.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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