Hydrogen and Copper Ion-Induced Molecular Reorganizations in Scorpionand-like Ligands. A Potentiometric, Mechanistic, and Solid-State Study

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...

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Bibliographic Details
Published in:	Inorganic chemistry Vol. 46; no. 14; pp. 5707 - 5719
Main 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
Format:	Journal Article
Language:	English
Published:	United States American Chemical Society 09-07-2007
Subjects:	Copper - chemistry Hydrogen - chemistry Hydrogen-Ion Concentration Ions - chemistry Kinetics Ligands Models, Molecular Molecular Structure Phosphorus Acids - chemistry Potentiometry Water - chemistry X-Ray Diffraction
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Summary:	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.
Bibliography:	ark:/67375/TPS-QPKCN9RG-3 istex:0AB1A211351B98D0E8BF2B1E52F484824D31C408 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	0020-1669 1520-510X
DOI:	10.1021/ic700643n