Peripheral Stepwise Degradation Of A Porphyrin J-Aggregate

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Inorganic Chemistry


For metalation of the acidic form of tetrakis(4-sulfonatophenyl)porphyrin (dianionic H₄TPPS₄) by Cu(II), the order of reagent mixing determines the rate and mechanism of CuTPPS₄ formation. When copper salts are added last, the kinetic profile is fit as a (pseudo)-first-order process. However, J-aggregates of the H₄TPPS₄ porphyrin are rapidly formed at pH similar to 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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