Dinitrogen release from arylpentazole: a picosecond time-resolved infrared, spectroelectrochemical, and DFT computational study.
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.
Department of Chemistry, University of Sheffield , Brook Hill, Sheffield, S3 7HF United Kingdom.
Peter
P
Portius
Martin
M
Davis
Rory
R
Campbell
František
F
Hartl
Qiang
Q
Zeng
Anthony J H M
AJ
Meijer
Michael
M
Towrie