Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, and CIRCMSB, viale Stagno d'Alcontres 31, 98166 Messina, Italy.
Inorg Chem. 2012 Oct 1;51(19):10074-6. doi: 10.1021/ic301570p. Epub 2012 Sep 13.
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.
对于酸性形式的四(4-磺酸钠苯基)卟啉(二价阴离子 H(4)TPPS(4))的铜(II)配位，试剂混合的顺序决定了 CuTPPS(4)形成的速率和机制。当最后添加铜盐时，动力学曲线拟合为（拟）一级过程。然而，当 Cu(II)盐先于卟啉加入溶液中时，在 pH~3 时迅速形成 H(4)TPPS(4)卟啉的 J-聚集体。随后的卟啉单元配位导致这些阵列通过拟零级动力学曲线解组装，表明金属离子在纳米结构的边缘进行攻击。
