Over the last decade molecular containers have been increasingly studied within the context of complex chemical systems. Herein we discuss selected examples from the literature concerning three aspects of this field: complex host-guest behaviour, adaptive transformations of molecular containers and reactivity modulation within them.
Many examples exist of biological
self-assembled structures that
restructure in response to external stimuli, then return to their
previous state over a defined time scale, but most synthetic investigations
so far have focused on systems that switch between states representing
energetic minima upon stimulus application. Here we report an approach
in which triphenylphosphine is used as a chemical fuel to maintain
CuI-based self-assembled metallosupramolecular architectures
for defined periods of time. This method was used to exert control
over the threading and dethreading of the ring of a pseudorotaxane’s
axle, as well as to direct the uptake and release of a guest from
a metal–organic host. Management of the amount of fuel and
catalyst added allowed for time-dependent regulation of product concentration.
A porphyrin-edged metal-organic tetrahedron forms host-guest complexes containing 1-4 equiv of fullerene C, depending on the solvent employed. The molecules of C were bound anticooperatively within well-defined pockets; an X-ray crystal structure of three fullerenes inside the tetrahedron was obtained. Electrochemical measurements revealed that the electron-accepting properties of the fullerenes inside the capsules were altered depending on the mode of encapsulation. The binding of multiple fullerenes was observed to increase the electron affinity of the overall cluster, providing a noncovalent method of tuning fullerene electronics.
A focused library of potential hydrogelators each containing two substituted aromatic residues separated by a urea or thiourea linkage have been synthesised and characterized. Six of these novel compounds are highly efficient hydrogelators, forming gels in aqueous solution at low concentrations (0.03–0.60 wt %). Gels were formed through a pH switching methodology, by acidification of a basic solution (pH 14 to ≈4) either by addition of HCl or via the slow hydrolysis of glucono‐δ‐lactone. Frequently, gelation was accompanied by a dramatic switch in the absorption spectra of the gelators, resulting in a significant change in colour, typically from a vibrant orange to pale yellow. Each of the gels was capable of sequestering significant quantities of the aromatic cationic dye, methylene blue, from aqueous solution (up to 1.02 g of dye per gram of dry gelator). Cryo‐transmission electron microscopy of two of the gels revealed an extensive network of high aspect ratio fibers. The structure of the fibers altered dramatically upon addition of 20 wt % of the dye, resulting in aggregation and significant shortening of the fibrils. This study demonstrates the feasibility for these novel gels finding application as inexpensive and effective water purification platforms.
The combination of a bent diamino(nickel(II) porphyrin) with 2-formylpyridine and Fe(II) yielded an Fe(II) 4 L6 cage. Upon treatment with the fullerenes C60 or C70 , this cage was found to transform into a new host-guest complex incorporating three Fe(II) centers and four porphyrin ligands, in an arrangement that is hypothesized to maximize π interactions between the porphyrin units of the host and the fullerene guest bound within its central cavity. The new complex shows coordinative unsaturation at one of the Fe(II) centers as the result of the incommensurate metal-to-ligand ratio, which enabled the preparation of a heterometallic cone-shaped Cu(I) Fe(II) 2 L4 adduct of C60 or C70 .
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