title: Connection of metallamacrocycles via dynamic covalent chemistry: a versatile method for the synthesis of molecular cages.
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.
authors.affiliation: Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland.
authors.forename: Anton
authors.initials: A
authors.lastname: Granzhan
authors.forename: Clément
authors.initials: C
authors.lastname: Schouwey
authors.forename: Thomas
authors.initials: T
authors.lastname: Riis-Johannessen
authors.forename: Rosario
authors.initials: R
authors.lastname: Scopelliti
authors.forename: Kay
authors.initials: K
authors.lastname: Severin
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D018360:Crystallography, X-Ray; D000081007:Cymenes; D008024:Ligands; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D039821:Monoterpenes / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D012413:Rubidium / Q000737:chemistry
chemical_list: D000447:Aldehydes; D002712:Chlorides; D000081007:Cymenes; D008024:Ligands; D047028:Macrocyclic Compounds; D039821:Monoterpenes; D009942:Organometallic Compounds; D011725:Pyridines; C007210:4-cymene; C035877:2,3-dihydroxypyridine; D012413:Rubidium; C032710:rubidium chloride