Synthesis of an Adaptable Molecular Barrel and Guest Mediated Stabilization of Its Metastable Higher Homologue

合成一种可适应性分子桶及其亚稳态高同系物的客体介导稳定化

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Abstract

Structural and functional modulation of three-dimensional artificial macromolecular systems is of immense importance. Designing supramolecular cages that can show stimuli mediated reversible switching between higher-order structures is quite challenging. We report here construction of a Pd(6) trifacial barrel (1) by coordination self-assembly. Surprisingly, barrel 1 was found to exhibit guest-responsive behavior. In presence of fullerenes C(60) and C(70), 1 unprecedentedly transformed to its metastable higher homologue Pd(8) tetrafacial barrel (2), forming stable host-guest complexes (C(60))(3)⊂2 and (C(70))(2)⊂2, respectively. Again, encapsulated fullerenes could be extracted from the cavity of 2 using 1,2-dichlorobenzene, leading to its facile conversion to the parent trifacial barrel 1. Such reversible structural interconversion between an adaptable molecular barrel and its guest stabilized higher homologue is an uncommon observation.

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