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1.
Phys Chem Chem Phys ; 21(44): 24592-24600, 2019 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-31665197

RESUMO

The rate coefficient for the possible reaction of OH radical with N2O was determined to be k1 < 1 × 10-17 cm3 molecule-1 s-1 between 253 and 372 K using pulsed laser photolysis to generate OH radicals and pulsed laser induced fluorescence to detect them. The rate coefficient for the reaction of NO3 radical with N2O was measured to be k2 < 5 × 10-20 cm3 molecule-1 s-1 at 298 K using a direct method that involves a large reaction chamber equipped with cavity ring down spectroscopic detection of NO3 and N2O5. Various tests were carried out ensure the accuracy of our measurements. Based on our measured upper limits, we suggest that these two reactions alter the atmospheric lifetime of N2O of ∼120 years by less than 4%.

2.
Dalton Trans ; 46(28): 8992-9009, 2017 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-28653065

RESUMO

Compared to divalent ruthenium coordination complexes, which are widely exploited as parts of multi-component photonic devices, optically active trivalent chromium complexes are under-represented in multi-metallic supramolecular architectures performing energy conversion mainly because of the tricky preparation of stable heteroleptic CrIII building blocks. We herein propose some improvements with the synthesis of a novel family of kinetically inert heteroleptic bis-terdentate mononuclear complexes, which can be incorporated into dinuclear rod-like dyads as a proof-of-concept. The mechanism and magnitude of intermetallic CrCr communication have been unraveled by a combination of magnetic, photophysical and thermodynamic investigations. Alternated aromatic/alkyne connectors provided by Sonogashira coupling reactions emerge as the most efficient wires for long-distance communication between two chromium centres bridged by Janus-type back-to-back bis-terdentate receptors.

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