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pH‐Dependent Excited‐State Properties of N,N‐di(2‐phosphonoethyl)‐1,4,5,8‐naphthalenediimide
Author(s) -
Rodrigues Magali A.,
Brochsztain Sérgio,
Barros Teresa C.,
Baptista Mauricio S.,
Politi Mario J.
Publication year - 1999
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1999.tb01946.x
Subject(s) - intersystem crossing , chemistry , protonation , photochemistry , flash photolysis , aqueous solution , fluorescence , titration , excited state , deprotonation , potentiometric titration , monomer , dissociation (chemistry) , reaction rate constant , kinetics , organic chemistry , polymer , ion , physics , electrode , quantum mechanics , nuclear physics , singlet state
— The effect of the protonation state of a novel aqueous soluble N,N'‐di(2‐phosphonoethyl)‐l,4,5,8‐naphthalene‐diimide (DPN) on its spectroscopic properties is studied. In aqueous solution DPN depicts linear Lambert‐Beer plots up to the solubility limits at pH 1.0, 7.1 and 10.1, in accordance with its solubilization as a monomer. A small increase in the extinction coefficients with pH is observed. Conversely a strong decrease in the fluorescence emission yields are observed with the increase in pH. These results are shown to originate from the distinct efficiencies of the intersystem crossing of DPN as a function of the net charge on the phosphono moieties. Accordingly, from the decrease in fluorescence emission, titration curves were obtained resulting in two pKa of –1.5 and 6.7 in agreement with the potentiometric analysis. In parallel monitoring the amount of heat deposited in the system shows an inverse pattern, that is, increase in the thermal tensing time‐resolved signal with pH. Laser flash photolysis and thermal Iensing data in the absence and presence of oxygen show the interplay of an intersystem crossing process with the protonation state of the dye. The changes in protonation from neutral to two‐ and four‐fold charged species are accompanied by an enhancing effect on the naphthalenediimide ring toward spin inversion (triplet formation) and consequently in different fluorescence yields