Avo, J, Parola AJ, Lima JC, Pina F, Cunha-Silva L.
2011.
Phase transition thermochromism based on C-H acidity of 4-alkylflavylium compounds in Pluronic F-127, 2011. Journal of Materials Chemistry. 21:16628-16637.
AbstractIn moderately acidic water/ethanol solutions, 7-(naphthalen-2-ylmethyl)-5,6-dihydrobenzo[c]xanthen12-ium perchlorate shows C-H proton acidity giving rise to an ethylenic base species, instead of the hydration products of the typical flavylium network of chemical reactions, hemiketal, cis-chalcone and trans-chalcone. The kinetics of this acid-base process is much slower, k(obs)(s(-1)) = 3.5 x 10(-3) + 0.16[H(+)], than those commonly observed for O-H deprotonation. In the presence of the triblock copolymer Pluronic F-127, the ethylenic base is dramatically stabilized shifting the pK(a) from 1.35 (in ethanol : water (1 : 1) to -0.35. Taking profit from the well-described temperature dependence of this polymer, a phase transition thermochromic system was achieved. The system was cycled between 5 and 35 degrees C with negligible changes in absorbance after 20 cycles.
Leydet, Y, Gavara R, Cunha-Silva L, Parola AJ, Pina F.
2011.
Phase-Dependent Photochromism of a Lactone-Stabilized Chromene from a Flavylium Reaction Network, 2011. Chemistry-a European Journal. 17:3663-3671.
AbstractNew trans-2-hydroxychalcones bearing a carboxylate group at position 2' (Ct(-)) were synthesized (compounds 2 and 3). These compounds lead to a network of chemical reactions depending on pH value, light, and solvent. In water, when the pH value is lowered, the ionized trans-chalcone is protonated and the flavylium cation AH(+) is formed at very acidic pH values through hemiketal B and cis-chalcone Cc, with global acidity constants of pK'(a) <= -1 and approximate to 0.1, respectively, for 2 and 3. The electron-acceptor character of the carboxylic substituent not only increases the observed acidity of the flavylium cation, but also decreases the rate of the ring-opening/closing from a subsecond timescale to hours relative to model compound 1 (without carboxylate). The photochemistry of the network was studied in detail by means of continuous irradiation, monitored by UV/Vis absorption and H-1 and C-13 NMR spectroscopic analysis. Although compound 3 is only slightly photoactive, compound 2 (Ct(-)) reacts in aqueous solutions (lambda(irr) = 313 nm) to form B- and Cc(-), with a global quantum yield of 0.15, and fully reverts back to Ct(-) with a rate constant of k = 6.7 x 10(-5) s(-1). The flavylium cation is no longer formed in methanol, and irradiation of Ct(-) leads to the formation of B- and the new lactone-trapped chromene species La. The formation of La takes place through a sequence of three photochemical steps: photoisomerization of Ct(-), photo-ring-closing reaction of Cc , and photolactonization of B-. Only the cis/trans isomerization and ring-closing reactions are thermally reversible on a timescale of seconds and hours, respectively. A photochromic system was achieved in rigid matrices of methanol (at 77 K) and 1-dodecanol (5 degrees C) by irradiating lactone La to give a red ortho-quinone allide through a photo-ring-opening reaction; the color disappears with a rate constant of k = 1.25 x 10(-2) s(-1) in 1-dodecanol at 5 degrees C.
Gomes, AC, Bruno SM, Gago S, Lopes RP, Machado DA, Carminatti AP, Valente AA, Pillinger M, Goncalves IS.
2011.
Epoxidation of cyclooctene using soluble or MCM-41-supported molybdenum tetracarbonyl-pyridylimine complexes as catalyst precursors. Journal of Organometallic Chemistry. 696:3543-3550., Number 22
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Neves, P, Gago S, Balula SS, Lopes AD, Valente AA, Cunha-Silva L, Almeida Paz FA, Pillinger M, Rocha J, Silva CM, Goncalves IS.
2011.
Synthesis and Catalytic Properties of Molybdenum(VI) Complexes with Tris(3,5-dimethyl-1-pyrazolyl)methane. Inorganic Chemistry. 50:3490-3500., Number 8
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