Template Control over Dimerization and Guest Selectivity of Interpenetrated Coordination Cages

被引:161
作者
Freye, Sabrina [1 ]
Michel, Reent [1 ]
Stalke, Dietmar [1 ]
Pawliczek, Martin [2 ]
Frauendorf, Holm [2 ]
Clever, Guido H. [1 ]
机构
[1] Univ Gottingen, Inst Inorgan Chem, D-37077 Gottingen, Germany
[2] Univ Gottingen, Inst Organ & Biomol Chem, D-37077 Gottingen, Germany
关键词
INTERLOCKED METALLOHELICATE; ENCAPSULATION; ANION; COMPLEXES; POLYHEDRA; BINDING; MOLECULES; DESIGN;
D O I
10.1021/ja403184a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We have previously shown that the self-assembly of dibenzosuberone-based bis-monodentate pyridyl ligands L-1 with Pd-11 cations leads to the quantitative formation of interpenetrated coordination cages [BF4@Pd4L81]. 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 [Pd2L42] is formed. Addition of the small anionic template Cl- permits dimerization, yielding the interpenetrated double cage [Cl@Pd4L82], whose enlarged outer pockets show a preference for the binding of large anions such as ReO4-.
引用
收藏
页码:8476 / 8479
页数:4
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