The complex network of chemical reactions of the compound 6-hydroxyflavylium perchlorate was studied by different techniques including UV-vis absorption spectrophotometry, stopped-flow, electrochemistry, and photochemistry. The network is characterized by the formation of a very reactive zwitterionic base as well as by p-quinoidal chalcones. The trans-chalcone is metastable in very acidic solutions and exhibits reversible redox reactions, allowing to introduce for the first time in the flavylium network an electrochemical input.

The network of chemical reactions of the compound 4'-methoxyflavylium was studied in the presence of SDS micelles, using stopped-flow, UV-vis absorption and flash photolysis techniques. The results were compared with analogous experiments carried out in water. The large stabilization of the flavylium cation onto the micelles was proven to be due to an increase in the rate of the dehydration reaction, rather than a decrease of the hydration reaction; the cis-trans isomerisation of the chalcone was not affected by the micelles. It is shown that SDS micelles can be considered as an external stimulus capable of changing the system from one state to another. (c) 2006 Elsevier B.V. All rights reserved.

Differently from water,effcient photochromism with a strong colour contrast has been observed for the multistate compound 7,4'- dihydroxyflavylium in the presence of cetyl trimethylammonium bromide ( CTAB) micelles. Two states are responsible for the photochromism: trans-chalcone ( inside the micelle) in the dark, and flavylium cation, AH(+), ( in bulk water) upon irradiation. The kinetics of the system was characterized by. ash photolysis and pH jumps. Evidence that the photochemical process leading to AH(+) occurs in the micelle was achieved. The best colour contrast is obtained at pH = 1.5, from a solution practically colourless in the dark, to an intense yellow upon irradiation ( quantum yield 0.4). The system is completely reversible with a lifetime of 38 min at room temperature, and exhibits a reasonable stability. A kinetic model capable of fitting the data from thermal entrance of the compound into the micelle, its ejection to bulk water upon irradiation and quantum yields of the photochemical process is proposed.

The compound 7,4'-dihydroxy-5-methoxyflavylium (dracoflavylium) was identified as the major red colorant in samples of the resin "dragon's blood", extracted from the tree Dracaena draco. The complex network of reversible chemical reactions that dracoflavylium undergoes in aqueous solution is fully described; for the first time, all the equilibrium constants that enable a complete characterisation of the system have been obtained (K'(a)=1.6 x 10(-4), K-a1 = 1.0 x 10(-4), K-a2 = 3.2 x 10(-8), K-Ct1 = 1.0 x 10(-7), K-Ct2 = 1.3 x 10(-10)). It is concluded that the red colour is due to a stable quinoid base, A, which is the major species at pH 4-7. It is further shown that this compound does not fit the commonly accepted definitions of anthocyanidin nor 3-deoxyanthocyanidin. Similarly to synthetic flavylium salts, the natural compound 7,4'-dihydroxy-5-methoxyflavylium gives rise to several species (multistate system) reversibly interconverted by external stimuli, such as pH.

The synthetic flavylium salt 6-hydroxy-4'-(dimethylamino)flavylium hexa. uorophosphate displays a set of pH-driven chemical reactions in aqueous solutions, involving the formation of hemiketal species and chalcones with cis and trans configurations. Such reactions were studied by steady-state and transient UV-Vis spectroscopy and by stopped-flow techniques. A novel and more generalized kinetic scheme is developed, in order to take account of possible acid/base pairs that occur in the network of chemical reactions as the pH is changed. It is found that the formation of the hemiketal species by hydration of the. avylium is slow, and it is not possible to isolate each process that leads to the formation of the cis-chalcone ( hydration and tautomerization reactions). The cis/trans isomerization reaction of cis-chalcone is slow, and the system takes several hours to reach equilibrium after a pH jump at room temperature. In basic conditions, negatively charged trans-chalcones are dominant. Comparison with other. avylium compounds shows that the hydration process is affected mainly by the amino group, while the hydroxyl group influences the tautomerization and isomerization reactions.

Photochromism of trans-4-(N,N-diethylamino)-2,4'-dihydroxychalcone, with formation of the photoproduct 7-(N,N-diethylamino)-4'-hydroxyflavylium, is promoted in the ionic liquid phase of a water/[bmim][PF6] biphasic system.

A strategy to obtain photochromism from the network of chemical reactions originated by flavyliurn compounds in solution is described. This strategy is particularly useful for flavyliurn salts bearing amino groups which give rise to a variety of beautiful colors but lack photochemistry in water. The trans-chalcone of 7-(N,Ndiethylamino)-4'-hydroxyflavylium interacts strongly with CTAB micelles defining a yellow dark state. Upon irradiation, the system switches to a pink-red state emerging from the flavylium cation that is formed inside the micelle and ejected to the bulk aqueous phase. The photochemical product reverts back to the transchalcone adduct with the micelle in the dark. The thermodynamics as well as the kinetics of the photochromic system were studied in detail. The best color contrast is obtained at pH = 4.25 with (D = 0.001 and a recovery lifetime of approximately 3 h. This photochromic system works with no need of changing the pH, which constitutes an important improvement over previously described systems dependent on pH jumps.

Two new components have been identified in an early sample prepared according to the original recipe of Perkin, and perhaps even by Perkin himself around 1860 - a new isomer of Perkin's mauveine B (designated as mauveine B2) together with a new mauveine compound (mauveine C) - and these compounds were synthesized again using starting materials chosen to reproduce Perkin's original synthesis and isolated by HPLC-DAD, identified by H-1 NMR, MS and their spectroscopic (UV/Vis and emission) and photophysical behaviour investigated.

Useful application of photochromic compounds as optical memories implies the existence of a large kinetic barrier between the forms interconverted by light. In the case of flavylium salts, the ground state isomerization barrier between the photoisomerizable chalcone isomers is shown to correlate with the electron donating ability of the substituents, measured by their effects in the H-1 NMR chemical shifts of the aromatic protons. Substitution with electron donating groups in ring A lowers the barrier while substitution at ring B has the opposite effect. However, in water, the observed increase is higher than expected in the case of compound 4', 9-dihydroxychalcone when compared with the analogous 4'-dimethylamino-9-hydroxychalcone, containing a better electron donating group in the same position. Our interpretation is that the water network is providing an efficient pathway to form tautomers. In acetonitrile, unlike water, the expected order is indeed observed: E-a( 4', 9-dihydroxychalcone) = 60 kJ mol(-1) < E-a ( 4'-dimethylamino-9-hydroxychalcone) = 69 kJ mol(-1).

The synthesis, potentiometric studies and photophysical properties of two new polyamine ligands (L1 and L2) possessing the dansyl chromophore were studied in aqueous 0.15 M NaCl. The compounds show the absorption and emissions bands characteristic of the dansylamide fluorophore and both present intramolecular excited state proton transfer at intermediate pH ranges. One of the ligands (L2) strongly coordinates Zn(II) leading to fluorescence quenching. A model compound (L3) of the dansyl moiety was also investigated. (c) 2006 Elsevier B.V. All rights reserved.