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|Title:||Photophysics of an Indigo Derivative (Keto and Leuco Structures) with Singular Properties||Authors:||Melo, J. Seixas de
Burrows, H. D.
Melo, M. J.
|Issue Date:||28-Dec-2006||Publisher:||American Chemical Society||Citation:||The Journal of Physical Chemistry A. 110:51 (2006) 13653-13661||Abstract:||Spectral and photophysical properties of the indigo derivative Cibalackrot in keto and reduced (leuco) forms were studied by absorption spectra, fluorescence and pulse radiolysis and compared with the structurally similar indigo. With the keto form of this dye, fluorescence (phiF = 0.76) and intersystem crossing (phiT = 0.11) are dominant, whereas with indigo, efficient internal conversion (phiIC = 0.99) is observed, probably involving proton transfer through intramolecular hydrogen bonds. With Cibalackrot, this pathway is blocked, supporting the above model for indigo. With the reduced form of Cibalackrot, more than 98% of the absorbed quanta are dissipated through S1 → S0 internal conversion, which contrasts with leuco-indigo, where fluorescence (phiF = 0.35), internal conversion (phiIC = 0.53) and intersystem crossing (phiT = 0.125) are found to be competitive. In addition, a synthetic precursor of Cibalackrot (preCiba) was also investigated. This has a rigid molecular structure (with a moiety identical to Cibalackrot and the other to indigo), but intra- or intermolecular proton transfer is allowed between adjacent carbonyl and N−H groups. With this precursor in its keto structure the photophysical parameters are generally very close to those of the keto form of indigo, and different from those of Cibalackrot. A more detailed investigation of the time-decay profiles of preCiba in dioxane (and with added water and D2O) has shown that these follow biexponential laws with a shorter component of 14−25 ps, which appears associated with a risetime at longer wavelength emissions (and to a positive preexponential at shorter emission wavelengths) and a longer lived (decay) component of 104−130 ps. In the steady-state spectra of preCiba, the variation with temperature reveals a blue shift of the emission maxima, which is interpreted as the presence (simultaneous emission) of two species (keto and enol) in the excited state. Indigo and deuterated indigo are also found to present a similar behavior. The overall data are interpreted as to be due to an excited-state process involving the proton transfer between keto and enol forms. Rate constants with values of 7 × 1010 s-1 for preCiba and 1.6 × 1011 s-1 for deuterated indigo were obtained. This inverse isotope effect is justified on the basis of the proposed model for proton-transfer excited-state deactivation.||URI:||http://hdl.handle.net/10316/10277||ISSN:||1089-5639||DOI:||10.1021/jp057451w||Rights:||openAccess|
|Appears in Collections:||FCTUC Química - Artigos em Revistas Internacionais|
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