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Redox‐Assisted Self‐Assembly of a Water‐Soluble Cyanido‐Bridged Mixed Valence {Co III /Fe II } 2 Square
Author(s) -
Alcázar Laura,
Aullón Gabriel,
Ferrer Montserrat,
Martínez Manuel
Publication year - 2016
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.201603482
Subject(s) - chemistry , redox , aqueous solution , valence (chemistry) , lability , electrochemistry , synthon , crystallography , cyclen , inorganic chemistry , analytical chemistry (journal) , stereochemistry , electrode , organic chemistry
The facile redox‐assisted assembly of a water‐soluble, extremely robust, cyanide‐bridged mixed‐valence [{Co III {(Me) 2 (μ‐ET)cyclen}} 2 {(μ‐NC) 2 Fe II (CN) 4 } 2 ] 2− square is reported. The preparation process involved the use of the enhanced lability of inert Co III synthons triggered by outer‐sphere redox processes. Characterization of the final compounds has been carried out by NMR, UV/Vis, electrochemistry, and ICP analyses. DFT calculations have been conducted to optimize a structure that has the same hydrodynamic radius as that obtained from DOSY experiments. The new compound is extremely robust, surviving in aqueous solution within the 0–12 pH range for months. The species shows a high affinity for both protons and hydroxo ions in aqueous medium.