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Selective Metal‐Cation Recognition by [2.2]Ferrocenophanes: The Cases of Zinc‐ and Lithium‐Sensing
Author(s) -
Otón Francisco,
Ratera Imma,
Espinosa Arturo,
Wurtz Klaus,
Parella Teodor,
Tárraga Alberto,
Veciana Jaume,
Molina Pedro
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901421
Subject(s) - zinc , lithium (medication) , metal , lithium metal , chemistry , inorganic chemistry , medicine , organic chemistry , electrode , electrolyte
Abstract The synthesis, electrochemical, optical, and cation‐sensing properties of [2.2]ferrocenophanes, in which the two ferrocene subunits are linked through two aldiminic or iminophosphorane moieties, are reported. The new compounds show remarkably selective cation‐sensing properties due to the presence of redox‐active units (ferrocene) and aza‐unsaturated functionalities that are able to act as putative cation‐binding sites. In this structural motif, the aldimine groups act as a highly selective binding site for Zn 2+ cations, whereas the iminophosphorane bridges display an unusually strong binding affinity towards Li + cations, which could be explained by an additional Li⋅⋅⋅Fe interaction. The X‐ray structure of the complex 4⋅ Li + as well as detailed NMR spectroscopic studies, both in solution and in the solid state, support this assessment. Experimental data and conclusions about the cation‐sensing capabilities of this family of compounds are supported by DFT calculations.