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1.
Inorg Chem ; 59(20): 14819-14826, 2020 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-33000943

RESUMO

With the exception of lithium, alkali metals do not react with elemental nitrogen either at ambient conditions or at elevated temperatures, requiring the search for alternative synthetic routes to their nitrogen-containing compounds. Here using a controlled decomposition of sodium azide (NaN3) at high pressure conditions, we synthesize two novel compounds, Na3(N2)4 and NaN2, both containing dinitrogen anions. NaN2 synthesized at 4 GPa might be the common intermediate in high-pressure solid-state metathesis reactions, where NaN3 is used as a source of nitrogen, while Na3(N2)4 opens a new class of compounds, where [N2] units accommodate a noninteger formal charge of 0.75-. This finding can dramatically extend the expected compositions in other group 1 and 2 metal-nitrogen systems. Electronic structure calculations show the metallic character for both compounds.

2.
Chemphyschem ; 18(10): 1385-1392, 2017 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-28220594

RESUMO

Nanoparticles of Ti3 O5 have been reported to show a permanent photoinduced phase transition at room temperature. This suggests that light-induced phase transformations of Ti3 O5 nanoparticles may be promising for technological applications. Here, we report a photoinduced semiconductor-to-metal phase transition from ß-Ti3 O5 to λ-Ti3 O5 nanoparticles at room temperature observed directly by time-resolved X-ray powder diffraction in a pump-probe setup. The results show a partial structural change, limited by differences between pumped and probed volumes, which persists a few microseconds after excitation. The first step in the relaxation back to the ground state can be described by a single exponential decay with time constant within microsecond timescales. Analysis of the change in lattice constants enables us to estimate an average temperature increase across the phase transition, consistent with a thermally driven process.

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