The assembly of a [2]semirotaxane from a half-dumbbell endowed with a pyrazine coordination site and a bis-Zn(II) porphyrin cage as a multisite ring is reported. The threading is allosterically driven by the coordination of silver(I) ions to the multiple binding sites of the cage linkers, as shown by NMR studies. Addition of chloride ions destabilizes [2]semirotaxane, leading to its disassembly into its cage and half-dumbbell components.
View Article and Find Full Text PDFA [2]rotaxane built around a multi-responsive bis-acridinium macrocycle has been synthesized. Structural investigation has confirmed the interlocked nature of the molecule, and MD simulations illuminated its conformational dynamics with atomic resolution. Both halochromic and redox-switching properties were explored to shed light on the mechanical response and electronic changes that occur in the bis-acridinium [2]rotaxane.
View Article and Find Full Text PDFThe photophysical characterization of four supramolecular complexes based on covalent cages , , , and , consisting in either two free-base porphyrins or one Zn(II) porphyrin and one free-base porphyrin connected by four flexible linkers of different lengths incorporating triazole binding sites, and their Ag(I) complexation are reported. The complexation processes have been followed by means of absorption and emission spectroscopies, and a comprehensive computational study explains the behavior of the free-base porphyrin-containing cages. Absorption and emission features have been interpreted on the bases of conformational changes, metalation processes, and modification of energy transfer efficiencies occurring in the different cases.
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