Peripheral Stepwise Degradation of a Porphyrin J-Aggregate

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• 作者：Ilaria Occhiuto ; Giovanna De Luca ; Mariachiara Trapani ; Luigi Mons霉 Scolaro ; Robert F. Pasternack
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：October 1, 2012
• 年：2012
• 卷：51
• 期：19
• 页码：10074-10076
• 全文大小：220K
• 年卷期：v.51,no.19(October 1, 2012)
• ISSN：1520-510X

文摘

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 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.