2-Styryl-1-benzopyrylium derivatives exhibit deeper hues and absorption spectra that are substantially red-shifted when compared with their 2-phenyl-1-benzopyrylium analogues. They follow the same pH and light-dependent network of chemical reactions previously described for 2-phenyl-1-benzopyrylium compounds. In this work, the photochromic properties of 7-hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium chloride are reported. This compound was fully characterized by UV-vis absorption, fluorescence emission, pH jumps, and flash photolysis, and its properties were compared with the analogue 7,4'-dihydroxyflavylium (7-hydroxy-2-(4-hydroxyphenyl)-1- benzopyrylium). The trans-chalcones of both compounds lacking the hydroxyl in position 2 were synthesized and used as model compounds since they exhibit cis-trans isomerization but cannot be involved in the other processes resulting from the ring closure. The transient absorption of two triplets attributed to the chalcones Ct/Ct(-), and a tautomer was detected by nanosecond flash photolysis, independent of the existence of the 2-hydroxyl substituent. The experimental results are compatible with the main formation of cis-chalcone from the singlet state. In the case of the styryl derivatives, the fraction of triplet formed from excitation of Ct is much higher, and the fraction of isomerization is much smaller. For this reason, the photochemistry of 7-hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium in water is much less efficient than that of its parent 7,4'-dihydroxyflavylium; however, in the presence of CTAB micelles, intense red colors can be obtained upon irradiation, confirming the usefulness of this family of compounds as photochromic systems.

A symmetric bis(flavylium) constituted by two 7-hydroxyflavylium moieties linked by a methylviologen bridge was synthesized. The thermodynamic and kinetics of the network of chemical reactions involving bis(flavylium) and the model compound 7-hydroxy-4'-methylflavylium was completely characterized by means of direct and reverse pH jumps (stopped flow) and flash photolysis. Both compounds follow the usual pH-dependent network of chemical reactions of flavylium derivatives. The equilibrium species of the model compound are the flavylium cation (acidic species) and the trans-chalcone (basic species) with an apparent pK(a)' = 2.85. In the case of the bis(flavylium) it was possible to characterize by (1)H NMR spectroscopy three species with different degrees of isomerization: all flavylium, flavylium-trans-chalcone, and all trans-chalcone. Representation of the time-dependent mole fraction distribution of these three forms after a pH jump from equilibrated solutions of all-flavylium cation (lower pH values) to higher pH values, shows that formation of trans-chalcone is not completely stochastic (two independent isomerizations), the isomerization of one flavylium showing a small influence on the isomerization of the other. The radical of the methyl viologen bridge is formed upon reduction of the bis(trans-chalcone) with dithionite. The system is reversible after addition of an oxidant in spite of the occurrence of some decomposition.

The multistate/multifunctional properties of 4'-hydroxyflavylium in a water/ I -n-butyl-3 -methyl-imidazolium hexalluorophosphate (fbmim][PF6]) biphasic system are described. The kinetics and thermodynamics of this flavylium salt have been fully characterised in aqueous solutions and compared to those obtained in [bmim][PF6]. The trans-chalcone is thermally more stable in the ionic liquid but shows efficient photoisomerisation to the cis-chalcone, allowing to define write-read-erase cycles in this biphasic system. (C) 2004 Elsevier B.V. All rights reserved.

The chemistry and photochemistry of 3',4'-(methylenedioxy)flavylium was studied by means of UV-Vis spectrophotometry, H-1 NMR, stopped flow, and continuous irradiation, in acidic and basic aqueous solutions. Six species were identified: the flavylium cation, AH(+); the hemiketal, B; the cis- and the trans-chalcones, Cc and Ct, and their ionized forms, Cc(-) and Ct(-). These species de. ne a multiequilibria network whose kinetics and thermodynamics were completely characterized. The two pairs of chalcones de. ne two coupled photochromic systems, respectively in acidic and basic media, both allowing cycles capable of writing, reading and erasing to be defined.