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  • Connection of metallamacrocycles via dynamic covalent chemistry: a versatile method for the synthesis of molecular cages.

Connection of metallamacrocycles via dynamic covalent chemistry: a versatile method for the synthesis of molecular cages.

Journal of the American Chemical Society (2011-04-19)
Anton Granzhan, Clément Schouwey, Thomas Riis-Johannessen, Rosario Scopelliti, Kay Severin
ABSTRACT

A modular approach for the synthesis of cage structures is described. Reactions of [(arene)RuCl(2)](2) [arene = p-cymene, 1,3,5-C(6)H(3)Me(3), 1,3,5-C(6)H(3)(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)RuCl(2)](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 Å(3). An amine exchange process with ethylenediamine allows the clean conversion of a dodecanuclear cage into a hexanuclear cage without disruption of the metallamacrocyclic structures.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Rubidium chloride, 99.95% trace metals basis
Sigma-Aldrich
Rubidium chloride, BioUltra, for molecular biology, ≥99.0% (AT)
Sigma-Aldrich
Rubidium chloride, 99.8% trace metals basis
Sigma-Aldrich
2,3-Dihydroxypyridine, 95%
Sigma-Aldrich
Rubidium chloride, ReagentPlus®, ≥99.0% (metals basis)