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

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• 作者：Peter Portius ; Martin Davis ; Rory Campbell ; Franti拧ek Hartl ; Qiang Zeng ; Anthony J. H. M. Meijer ; Michael Towrie
• 刊名：Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：December 5, 2013
• 年：2013
• 卷：117
• 期：48
• 页码：12759-12769
• 全文大小：532K
• 年卷期：v.117,no.48(December 5, 2013)
• ISSN：1520-5215

文摘

p-(Dimethylamino)phenyl pentazole, DMAP-N₅ (DMAP = Me₂N鈥揅₆H₄), 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 (蟿 = 82 卤 4 ps), while DMAP-N and DMAP-N₃ (S₀) are generated as double and single N₂-loss photoproducts with 畏 鈮?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 (E_1/2 = +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.