Hydrogen and copper ion-induced molecular reorganizations in scorpionand-like ligands. A potentiometric, mechanistic, and solid-state study |
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Authors: | Verdejo Begoña Ferrer Armando Blasco Salvador Castillo Carmen Esther González Jorge Latorre Julio Máñez M Angeles Basallote Manuel García Soriano Conxa García-España Enrique |
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Institution: | Departamento de Química Inorgánica, Instituto de Ciencia Molecular, Universidad de Valencia, Edificio de Institutos de Paterna, Apdo 22085, 46071 Valencia, Spain. |
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Abstract: | Two aza scorpionand-like macrocycles (L2 and L3) have been prepared. L2 consists of a tren amine with two of its arms cyclizized with a 2,6-bis(bromomethyl)pyridine. In L3, the remaining pendant arm has been further functionalized with a fluorophoric naphthalene group. X-ray data on the compounds H(L3)]ClO4.H2O (1) and H3(L3)](H2PO4)3.H2O (2) as well as solution studies (pH-metry, UV-vis, and fluorescence data) show the movement of the pendant arm as a result of the protonation degree of the macrocycles and of the formation of intramolecular hydrogen bonds. X-ray data on the complexes Cu(L2)](ClO4)2]2.H2O (3) and Cu(L3)](ClO4)2 (4) and solution studies on Cu2+ coordination show the implication of the nitrogen of the arm in the binding to the metal ion. Kinetic studies on the decomposition and formation of the Cu2+ complexes provide additional information about the pH-dependent molecular reorganizations. Moreover, the obtained information suggests that the kinetics of the tail on/off process is essentially independent of the lability of the metal center. |
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