Connection of Metallamacrocycles via Dynamic Covalent Chemistry: A Versatile Method for the Synthesis of Molecular Cages
A modular approach for the synthesis of cage structures is described. Reactions of [(arene)RuCl2]2 [arene = p-cymene, 1,3,5-C6H3Me3, 1,3,5-C6H3(i-Pr)3] with formyl-substituted 3-hydroxy-2-pyridone ligands provide trinuclear metallamacrocycles with pendant aldehyde groups. Subsequent condensation reactions with di- and triamines give molecular cages with 3, 6, or 12 Ru centers in a diastereoselective and chemoselective (self-sorting) fashion. Some of the cages can also be prepared in one-pot reactions by mixing [(arene)RuCl2]2 with the pyridone ligand and the amine in the presence of base. The cages were comprehensively analyzed by X-ray crystallography. The diameter of the largest dodecanuclear complex is 3 nm; the cavity sizes range from 290 to 740 Å3. An amine exchange process with ethylenediamine allows the clean conversion of a dodecanuclear cage into a hexanuclear cage without disruption of the metallamacrocyclic structures.
Keywords: Supramolecular Triangular Hosts ; Metal-Organic Polyhedra ; Der-Waals Nanocapsules ; Coordination Cages ; Polar-Solvents ; Hydrogen-Bonds ; 12-Metallacrown-3 Complexes ; Boronate Esterification ; Selective Extraction ; Guest Encapsulation
Record created on 2011-04-15, modified on 2016-08-09