RESUMEN
Polymers with all mechanically interlocked rings, such as linear [n]catenanes, have great potential as functional materials due to possible higher degrees of freedom that may contribute to their flexibility but remain elusive. All the synthetic methods used to prepare such a polymer yield mixtures of products. In the absence of higher molecular weight linear [n]catenanes, emphasis on synthesizing low molecular weight oligomers is being pursued. Here, we have described the synthesis of a linear [5]catenane by post-functionalizing a Co(III) templated [2]catenane having a pyridine-diamide unit free for further metal ion coordination. Two molecules were synthesized with suitable threading groups: one, two terminal azide groups, and two, with two terminal alkyne groups to form two [3]pseudorotaxane utilizing Co(III) coordination. These units were then joined, forming a macrocycle, using click reaction, giving the desired metalated linear [5]catenane in 40 % yield. Removal of metal ions leads to linear [5]catenane. In addition, the formation of linear [3] and [2]catenane are also observed. All synthesized structures have been isolated by column chromatographic technique and characterized by 1H-NMR, 13C-NMR, and mass spectroscopy.
RESUMEN
Design and synthesis of higher order catenane are unexpectedly complex and involve precise cooperation among the precursors overcoming competing and opposing interactions. We achieved synthesis of [2], linear [3], radial [4] in a one-pot reaction by consecutive ring closing through click reactions. This synthesis gave three isolable products due to two, four, and six-click reactions between suitable coupling partners. Yields of the isolate templated-catenane decrease from lower to higher-ordered catenane (40 %, 12 %, and 4 %), probably due to the bite angle as well as the flexibility of the reacting partners. Removal of templating cobalt(III) ion leads to the formation of fully organic [2], linear [3], and radial [4]catenane. These synthesized catenanes were purified by column chromatography and characterized by 1H-NMR, 13C-NMR, and ESI-MS spectroscopy. The synthesized catenanes have free binding sites suitable for post-functionalization and may be used for the synthesis of higher-ordered catenane.