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Template Control over Dimerization and Guest Selectivity of Interpenetrated Coordination Cages

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posted on 19.02.2016, 06:22 authored by Sabrina Freye, Reent Michel, Dietmar Stalke, Martin Pawliczek, Holm Frauendorf, Guido H. Clever
We have previously shown that the self-assembly of dibenzosuberone-based bis-monodentate pyridyl ligands L1 with PdII cations leads to the quantitative formation of interpenetrated coordination cages [BF4@Pd4L18]. 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 L2 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 [Pd2L24] is formed. Addition of the small anionic template Cl permits dimerization, yielding the interpenetrated double cage [Cl@Pd4L28], whose enlarged outer pockets show a preference for the binding of large anions such as ReO4.