Template control over dimerization and guest selectivity of interpenetrated coordination cages
| Autor: | Martin Pawliczek, Reent Michel, Guido H. Clever, Sabrina Freye, Dietmar Stalke, Holm Frauendorf |
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| Rok vydání: | 2013 |
| Předmět: |
Steric effects
010405 organic chemistry Ligand Stereochemistry Aryl Allosteric regulation Substituent General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Chloride Catalysis 0104 chemical sciences 3. Good health chemistry.chemical_compound Crystallography Colloid and Surface Chemistry Monomer chemistry medicine Selectivity medicine.drug |
| Zdroj: | Journal of the American Chemical Society. 135(23) |
| ISSN: | 1520-5126 |
| Popis: | We have previously shown that the self-assembly of dibenzosuberone-based bis-monodentate pyridyl ligands L(1) with Pd(II) cations leads to the quantitative formation of interpenetrated coordination cages [BF4@Pd4L(1)8]. The BF4(-) anion inside the central cavity serves as a template, causing the outer two pockets to show a tremendous affinity for allosteric binding of two small chloride anions. Here we show that derivatization of the ligand backbone with a bulky aryl substituent allows us to control the dimerization and hence the guest-binding ability of the cage by the choice of the templating anion. Steric constraints imposed by L(2) prevent the large BF4(-) anion from serving as a template for the formation of interpenetrated double cages. Instead, a single isomer of the monomeric cage [Pd2L(2)4] is formed. Addition of the small anionic template Cl(-) permits dimerization, yielding the interpenetrated double cage [Cl@Pd4L(2)8], whose enlarged outer pockets show a preference for the binding of large anions such as ReO4(-). |
| Databáze: | OpenAIRE |
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