The construction of catenanes, comprised of between two and seven interlocked rings, has been achieved. Two tris-1,5-naphtho-57-crown-15 macrocycles template the formation of cyclobis(paraquat-4,4'-biphenylene) to give a [3]catenane, which acts as a template for the construction of one and then another cyclobis(paraquat-p-phenylene) to give a [4]- and [5]catenane (Olympiadane). When high pressure was used in these templated syntheses, a [6]- and [7]catenane, as well as a [5]catenane that is topologically isomeric with Olympiadane, were also obtained. X-ray analyses of the [3]-, [5]-, and [7]catenanes reveal an optimum use of electrostatic, π-π stacking, [C- H···π] interactions, and [C-H···O] hydrogen bonds in the organization of the component rings within the molecules. Noteworthy in the [7]catenane structure is the location of four of the PF6/- anions within voids present in the 20+ ion. Temperature-dependent 1H NMR spectroscopic studies and electrochemical investigations have revealed the dynamic and redox behavior of these catenanes in solution.
Amabilino, D.B., Ashton, P.R., Balzani, V., Boyd, S.E., Credi, A., Lee, J.Y., et al. (1998). Oligocatenanes made to order. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 120(18), 4295-4307 [10.1021/ja9720873].
Oligocatenanes made to order
Balzani V.;Credi A.;Venturi M.;
1998
Abstract
The construction of catenanes, comprised of between two and seven interlocked rings, has been achieved. Two tris-1,5-naphtho-57-crown-15 macrocycles template the formation of cyclobis(paraquat-4,4'-biphenylene) to give a [3]catenane, which acts as a template for the construction of one and then another cyclobis(paraquat-p-phenylene) to give a [4]- and [5]catenane (Olympiadane). When high pressure was used in these templated syntheses, a [6]- and [7]catenane, as well as a [5]catenane that is topologically isomeric with Olympiadane, were also obtained. X-ray analyses of the [3]-, [5]-, and [7]catenanes reveal an optimum use of electrostatic, π-π stacking, [C- H···π] interactions, and [C-H···O] hydrogen bonds in the organization of the component rings within the molecules. Noteworthy in the [7]catenane structure is the location of four of the PF6/- anions within voids present in the 20+ ion. Temperature-dependent 1H NMR spectroscopic studies and electrochemical investigations have revealed the dynamic and redox behavior of these catenanes in solution.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
