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Updated: May 18, 2026

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
Published on: July 19, 2019
Peripheral stepwise degradation of a porphyrin J-aggregate
Ilaria Occhiuto1, Giovanna De Luca, Mariachiara Trapani
1Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, and CIRCMSB, viale Stagno d'Alcontres 31, 98166 Messina, Italy.
Abstract:
For metalation of the acidic form of tetrakis(4-sulfonatophenyl)porphyrin (dianionic H(4)TPPS(4)) by Cu(II), the order of reagent mixing determines the rate and mechanism of CuTPPS(4) formation. When copper salts are added last, the kinetic profile is fit as a (pseudo)-first-order process. However, J-aggregates of the H(4)TPPS(4) porphyrin are rapidly formed at pH ~ 3 when Cu(II) salts are incorporated in solution prior to porphyrin addition. The subsequent porphyrin units metalation leads to the disassembling of these arrays via a pseudo-zero-order kinetic profile, suggesting an attack of the metal ion at the rims of the nanostructure.
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