Inner Core Structure Responds to Communication between Nanocapsule Walls

Cave, Gareth W. V.; Antesberger, Jochen; Barbour, Leonard J.; McKinlay, Robert M.; Atwood, Jerry L.

doi:10.1002/anie.200460711

Cited by 118 publications

(55 citation statements)

References 25 publications

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“…1) could behave as a multidentate ligand. Interestingly, close inspection of the previously reported hydrogen-bonded solid-state hexameric structure 3 shows that there are 24 regioselective chelate sites on its framework (29). Deprotonation from the upper-rim phenol groups within these assemblies for metal-ion retroinsertion would result in the desired structural preservation of the hexameric capsule while introducing useful inorganic functionality.…”

Section: Resultsmentioning

confidence: 89%

“…The large coordination capsule 2 represents the inorganic counterpart of the hydrogen-bonded structure 3 (29). Remarkably, capsules 2 and 3 exhibit similar metrical parameters and dimensions, even in the face of the loss of 48 protons and the gain of 24 Cu(II) ions (Fig.…”

Section: Resultsmentioning

confidence: 97%

“…The resorcin [4]arene and pyrogallol [4]arene macrocycles have been shown to have a great deal of robustness in forming large spheroid hexameric cage assemblies in both solution and solid state (26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37)(38). Indeed, this property has inspired and contributed to numerous theoretical and experimental studies of its hostguest relationships.…”

Section: Resultsmentioning

confidence: 99%

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Supramolecular blueprint approach to metal-coordinated capsules

McKinlay

Cave

Atwood

2005

Proc. Natl. Acad. Sci. U.S.A.

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199

182

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An important problem in designing any large network is the assembly of systems that are resilient to change. From a chemical point of view, an analogy can be used where one requires supramolecular assemblies to maintain their dimensionality combined with limited structural perturbation in response to variation in its intermolecular framework. The identification of hydrogenbonded framework patterns within experimentally known supramolecular assemblies that are structurally robust to disruption and selective hydrogen substitution are envisioned to act as a supramolecular blueprint or template for metal-ion retroinsertion. Here, we report the formation of a large neutral discrete pseudo-spherical coordination capsule assembled from 6 pyrogallol[4]arene ligands and 24 Cu(II) metal ions. Amazingly, this coordination capsule is structurally analogous to its hydrogenbonded counterpart. This result shows a robust ability of pyrogallol[4]arene molecules to self-assemble into large hexameric cage structures from either the hydrogen-bonding or metal-ligand coordination process. The identification of robust supramolecular assemblies that conserve their structure in response to interchangeability between hydrogen-bonded networks for metal coordination, or inversely, represents an important advancement in supramolecular design.coordination ͉ self-assembly ͉ hexamer I nspired by the architectural beauty and robustness found within nature, the design of large multicomponent spheroid cage assemblies on the nanometer scale is becoming increasing feasible. These large supramolecular architectures often resemble and conform to the simple geometrical shapes described by Platonic or Archimedean solids (1). Indeed, such structural morphologies have attracted tremendous interest because of their practical applications for encapsulating various guest molecules (2). Synthetic chemists have principally relied on various self-assembly methods in their construction, such as hydrogen bonds (3) or metal-ligand coordination (4), although some notable covalent methods have recently been reported (5).A popular strategy for designing large multicomponent cage assemblies is the metal-directed self-assembly approach, advocated chiefly by Fujita and coworkers (6-9) and Stang and coworkers (10-12). This method has mainly focused on the geometrical permutation of various triangular pyridine-like bridging ligands driven by coordination to cis-protected Pd metal centers. Nevertheless, for the construction of discrete assemblies with large molecular cavities, the molecular paneling approach by Fujita and coworkers (13) has received the most success. Indeed, an amazingly large discrete functionalized spherical coordination network assembled from 12 metal ions and 24 exo-multidentate ligands was recently reported (14). However, an inherent complication of using n-dimensional pyridine-like spacer multidentate ligands in coordination is the resultant high positive charge combined with porous surfaces within these supramolecular assemblies. The counterions us...

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Supramolecular blueprint approach to metal-coordinated capsules

McKinlay

Cave

Atwood

2005

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

199

182

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“…Recently particular interest has been focused on the use of pyrogallolarenes as inclusion hosts, molecular capsules, 3,4 selective receptors, molecular sensors, [5][6][7][8] and novel building blocks for supramolecaular chemistry.…”

Section: Introductionmentioning

confidence: 99%

Microwave Assisted Efficient Synthesis and Crystal Structures of O‐Hexadecalkylated Pyrogallol[4]arenes

Chen

Yan

2009

Chin. J. Chem.

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Under microwave irradiation alkylation reactions of sixteen phenolic hydroxyl groups in tetra(p-hydroxyphenyl)pyrogallol [4]arene with alkylating reagents such as n-butyl iodide, benzyl chloride, and ethyl α-chloroacetate were finished quickly in one step to give the fully O-alkylated products. The X-ray single crystal diffraction showed that the three peralkylated pyrogallol [4]arenes existed in rctt (cis-trans-trans) configuration.

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“…Supramolecular chemists have exploited hydrogen-bonding interactions, dynamic covalent chemistry, and metal-ion coordination to assemble a wonderful array of molecular topologies such as nanospheroids, [1][2][3][4][5][6] tubules, [7,8] and various knots. [9] In this context, any closed surface can be expressed topologically as a torus containing a finite number of holes.…”

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confidence: 99%