The decomposition of triphenylimidazole-para-acetate follows specific base catalysis and can be conveniently followed by fluorescence.

The kinetics of the decomposition reaction of 4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl acetate (1) in basic alcoholic media was investigated, using a simple fluorescence (FL) spectrophotometric procedure. The process was conveniently studied using FL, since the triphenylimidazole-derived ester 1 and its reaction products (the corresponding phenol 2 and phenolate 2- ) are all highly fluorescent (ΦFL  > 37%). By carefully selecting excitation and emission wavelengths, observed rate constants k1 in the order of 10-3 to 10-2  s-1 were obtained from either reactant consumption (λex  = 300 nm, λem  = 400 nm) or product formation (λex  = 350 nm, λem  = 475 nm); these were shown to be kinetically equivalent. Intensity-decay time profiles also gave a residual FL intensity parameter, shown to be associated to the distribution of produced species 2 and 2- , according to the basicity of the medium. Studying the reaction in both methanol (MeOH) and isopropanol (iPrOH), upon addition of HO- , provided evidence that the solvent's conjugate base is the active nucleophilic species. When different bases were used (tBuO- , HO- , DBU and TEA), bimolecular rate constants kbim ranging from 4.5 to 6.5 L mol-1  s-1 were obtained, which proved to be non-dependent on the base pKaH , suggesting specific base catalysis for the decomposition of 1 in alcoholic media.

Spectroscopic Studies on the Interaction of Metallic Ions with an Imidazolyl-Phenolic System.

A fluorescent imidazolyl-phenolic compound was applied on the detection of metallic species (Cu(2+), Al(3+), Cr(3+) and Fe(3+)) in a CH3CN/H2O (95/5, v/v) media. The presence and concentration of these cations altered significantly the emission profile of the probe, mainly lowering the signal intensity at 466 nm, while a new emission band around 395 nm appeared (for the trivalent ions). These results were rationalized as a combination of collisional quenching (KSV in the 10(3)-10(4) L mol(-1) range) and formation of a coordinated compound. The later disrupts the Excited State Intramolecular Proton Transfer that regulates the keto-enol tautomerism originally present on the free probe. Since the quenching efficiency and the obtained emission profiles are drastically different for Cu(2+) and Fe(3+) ions, this allows their differential recognition.