Synthesis and Photophysics of a 1-Pyrenyl Substituted 2‘-Deoxyuridine-5-Carboxamide Nucleoside:  Electron Transfer Products as CIS INDO/S Excited States

Abstract

This paper reports results of the synthesis and photophysical study of 5-( N -carboxy-1-aminopyrenyl)-2‘-deoxyuridine (PA-dU) and its spectroscopic model N -acetyl-1-aminopyrene (PA-Ac). Absorbance and emission spectra, emission quantum yields, and emission lifetimes are reported for both compounds in three solvents. The data show that the emission yield quenching of PA-dU relative to PA-Ac varies from 95 to 99% in the solvent series THF, MeCN, and MeOH. In contrast to the monoexponential kinetics for (π,π*) 1 emission from PA-Ac, the (π,π*) 1 emission from the PA-dU nucleoside decays with two lifetimes in THF and three in MeCN and MeOH. The multiexponential emission decays are likely due to the presence of multiple nucleoside conformers. The average (π,π*) 1 lifetimes for PA-dU in THF, MeCN, and MeOH are, respectively, 4.8, 2.7, and 0.55 ns and correspond to lifetime quenching values of 58, 81, and 96%, respectively. The lifetime quenching values for PA-dU in THF and MeCN do not agree with the emission yield quenching values in these solvents of, respectively, 95 and 96%. Thus in these two solvents the emitting states for PA-dU have lower radiative rates than do the emitting states for PA-Ac in the same solvents. However, for PA-dU in MeOH the lifetime quenching percentages of 96% over the 380−440 nm range and 98% over the 405−440 nm range are in good agreement with the emission yield quenching value of 99% in this solvent. Additionally, the emission spectrum of PA-dU in MeOH matches the (π,π*) emission spectrum of PA-Ac in MeOH, while the emission spectra of PA-dU in THF and MeCN do not match the corresponding spectra of PA-Ac. Thus choice of solvent tunes the electronic nature and the radiative rate of the emitting state in PA-dU. Emission quenching in PA-dU is assigned to intramolecular electron transfer (ET), and the 550−600 nm emission region of PA-dU reflects the relaxation dynamics of the pyrene •+ /dU •- ET product. Strikingly emission lifetimes in this spectral region in all three solvents are extremely short, ≤100 ps. CIS INDO/S computations of the excited states for the 5-( N -carboxy-1-aminopyrenyl)-1-methyluracil (PA-U Me ) model show that two factors are major contributors to the variation in ET product (ET 1 ) energy among the eleven PA-U Me conformers identified. The first is the energy of the uracil LUMO (a redox effect), and the second is the pyrenyl/U Me subunit separation distance (a Coulombic effect). Importantly, the dihedral angle between the bridging carbonyl and the C5−C4 bond in U Me is strongly correlated with the energy of the uracil LUMO ( R = 0.94) and thus with the ET 1 energy. Finally, quantitative study of the energy of the ET 1 state versus pyrenyl/U Me separation distance shows a smooth x -1 increase in ET 1 energy as the separation distance increases ( R = 0.9994). Additionally, the extrapolated ET 1 energy at infinite subunit separation equals the difference between the LUMO and HOMO energies.