Dinitrogen Release from Arylpentazole: A Picosecond Time-Resolved Infrared, Spectroelectrochemical, and DFT Computational Study

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Portius, P. ; Davis, M. ; Campbell, R. ; Hartl, F. ; Zeng, Q. ; Meijer, A.J.H.M. ; Towrie, M. (2013)
  • Publisher: American Chemical Society

p-(Dimethylamino)phenyl pentazole, DMAP-N5 (DMAP = Me2N–C6H4), was characterized by picosecond transient infrared spectroscopy and infrared spectroelectrochemistry. Femtosecond laser excitation at 310 or 330 nm produces the DMAP-N5 (S1) excited state, part of which returns to the ground state (τ = 82 ± 4 ps), while DMAP-N and DMAP-N3 (S0) are generated as double and single N2-loss photoproducts with η ≈ 0.14. The lifetime of DMAP-N5 (S1) is temperature and solvent dependent. [DMAP-N3]+ is produced from DMAP-N5 in a quasireversible, one-electron oxidation process (E1/2 = +0.67 V). Control experiments with DMAP-N3 support the findings. DFT B3LYP/6-311G** calculations were used to identify DMAP-N5 (S1), DMAP-N3+, and DMAP-N in the infrared spectra. Both DMAP-N5 (S1) and [DMAP-N5]+ have a weakened N5 ring structure.
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