Hydrogen and Copper Ion-Induced Molecular Reorganizations in Scorpionand-like Ligands. A Potentiometric, Mechanistic, and Solid-State Study
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- 作者：Begoñ ; a Verdejo ; Armando Ferrer ; Salvador Blasco ; Carmen Esther Castillo ; Jorge Gonzá ; lez ; Julio Latorre ; M. Angeles Má ; ñ ; ez ; Manuel Garcí ; a Basallote ; Conxa Soriano ; Enri
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：July 9, 2007
- 年：2007
- 卷：46
- 期：14
- 页码：5707 - 5719
- 全文大小：275K
- 年卷期：v.46,no.14(July 9, 2007)
- ISSN：1520-510X
文摘
Two aza scorpionand-like macrocycles (L2 and L3) have been prepared. L2 consists of a tren amine with two ofits arms cyclizized with a 2,6-bis(bromomethyl)pyridine. In L3, the remaining pendant arm has been furtherfunctionalized 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 movementof the pendant arm as a result of the protonation degree of the macrocycles and of the formation of intramolecularhydrogen bonds. X-ray data on the complexes [Cu(L2)](ClO4)2]2·H2O (3) and [Cu(L3)](ClO4)2 (4) and solution studieson Cu2+ coordination show the implication of the nitrogen of the arm in the binding to the metal ion. Kinetic studieson the decomposition and formation of the Cu2+ complexes provide additional information about the pH-dependentmolecular reorganizations. Moreover, the obtained information suggests that the kinetics of the tail on/off processis essentially independent of the lability of the metal center.