Syntheses of metallo-pseudorotaxanes, rotaxane and post-synthetically functionalized rotaxane: A comprehensive spectroscopic study and dynamic properties

Abstract

Herein, a bis-amido tris-amine macrocycle and five bipyridine-based bidentate chelating ligands were investigated towards various divalent transition metal ion (NiII, CoII, CuII, and ZnII)-templated syntheses of metallo [2]pseudorotaxanes. The formation of these ternary complexes was elucidated via different spectroscopic techniques such as ESI-MS, absorption spectroscopy, EPR spectroscopy, and single-crystal X-ray diffraction studies wherever possible. Azide-terminated NiII, CoII, CuII, ZnII-templated [2]pseudorotaxanes were explored to generate [2]rotaxane, ROT, via reaction with an alkyne-terminated triphenylene unit as a stopper under the mild reaction condition of the CuI-catalyzed azide-alkyne cycloaddition reaction. NiII-templated [2]pseudorotaxane was found to be the best precursor towards the high-yield synthesis of ROT. The interpenetrative nature of the center piece in metal-free rotaxane was also established through various spectroscopic techniques such as ESI-MS and 1D and 2D (COSY, NOESY, ROESY, and DOSY) NMR spectroscopy. Furthermore, ROT was functionalized via tri-acetylation as AcROT to incorporate three tertiary amides at the tris-amine centers; this AcROT exhibited rotamer-induced molecular motions in an interpenetrated system via the formation of multiple conformers/co-conformers. Additionally, the existence of multiple rotamers was established via variable-temperature NMR spectroscopic studies. Li+ and 12-crown-4 were found to be suitable for the reversible conformation/co-conformation fixation of tri-acetylated bis-amido tris-amine macrocyclic wheel-based rotaxane.