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Issue 30, 2018
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Efficient intersystem crossing in 2-aminopurine riboside probed by femtosecond time-resolved transient vibrational absorption spectroscopy

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Abstract

The photophysical dynamics of 2-aminopurine riboside (2APr) in CHCl3 have been studied following excitation at λpump = 310 nm by means of femtosecond transient vibrational absorption spectroscopy (TVAS) aided by quantum chemical density functional theory (DFT) and ab initio calculations. The experiments identified numerous vibrational marker bands in the regions of the NH2 stretch and the 2AP ring vibrations which could be assigned to the bleach of the S0 electronic ground state (GS) and to transient populations in the 1ππ* and 3ππ* excited electronic states. The temporal evolution of the transient vibrational bands shows that the decay of the 1ππ* population is accompanied by a partial recovery of the GS and a concurrent population of the 3ππ* state with a time constant of τ2 = 740 ± 15 ps. The ensuing electronic relaxation is concluded to proceed via the 1nπ* state as intermediate state. The absence of observable transient vibrational bands of this state hints at an upper limit for its lifetime of τ < 100 ps. The triplet quantum yield is found to be ϕT = 0.42 ± 0.07.

Graphical abstract: Efficient intersystem crossing in 2-aminopurine riboside probed by femtosecond time-resolved transient vibrational absorption spectroscopy

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Article information


Submitted
26 Apr 2018
Accepted
11 Jul 2018
First published
12 Jul 2018

Phys. Chem. Chem. Phys., 2018,20, 20033-20042
Article type
Paper

Efficient intersystem crossing in 2-aminopurine riboside probed by femtosecond time-resolved transient vibrational absorption spectroscopy

H. Böhnke, K. Röttger, R. A. Ingle, H. J. B. Marroux, M. Bohnsack, A. J. Orr-Ewing and F. Temps, Phys. Chem. Chem. Phys., 2018, 20, 20033
DOI: 10.1039/C8CP02664E

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