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Anion‐Templated Formation of Supramolecular Multinuclear Assemblies
Author(s) -
Wezenberg Sander J.,
EscuderoAdán Eduardo C.,
BenetBuchholz Jordi,
Kleij Arjan W.
Publication year - 2009
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.200900528
Subject(s) - supramolecular chemistry , chemistry , titration , ligand (biochemistry) , self assembly , nuclear magnetic resonance spectroscopy , ion , crystallography , stereochemistry , inorganic chemistry , combinatorial chemistry , organic chemistry , crystal structure , biochemistry , receptor
Anion meets host(s) : Lewis acidic zinc(II)‐based salphen complexes have been found to interact strongly with various anions both in solution as well as in the solid state. A biologically relevant model anion (acetate, shown in red) has been exploited to serve as a molecular template for the synthesis of multinuclear Zn assemblies (Zn shown in green) with a short metal–metal distance, and consequently, resembles in part the metal‐ion proximity found in a range of multimetallic enzymes.The use of anions as supramolecular building motifs is reported herein. The interaction of various anions with [Zn(salphen)] complexes (salphen= N , N′ ‐phenylenebis(salicylideneimine)) has been studied, with a particular focus on assembly formation in the presence of acetate anions. Strong association of the latter with the Zn metal centre of the salphen complex was quantified by UV/Vis titration studies. The [Zn(salphen)]–OAc assemblies were further characterized by NMR spectroscopy and X‐ray analysis and revealed that the acetate anions can function as bridging modules between two [Zn(salphen)] units. The binding strength of a second complex to the acetate anion may be regulated by the substitution pattern of the salphen ligand. The anion‐templated assembly formation was further demonstrated by the supramolecular synthesis of a trinuclear Zn 3 assembly. These results hold promise for the directed assembly formation of [Zn(salphen)] complexes with biologically relevant carboxylates, such as amino acids, and potentially new bio‐sensing materials.