Multicomponent Dynamic Covalent Assembly of a Rhombicuboctahedral Nanocapsule

Liu, Yong; Liu, Xuejun; Warmuth, Ralf

doi:10.1002/chem.200701067

Cited by 114 publications

(53 citation statements)

References 73 publications

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“…We identify only one plausible organic cage topology for this system, co-workers using a tetratopic cavitand and a triphenylamine (although no crystal structure was reported for this experiment) 32 and two examples using porphyrin building blocks Fig. 10 The tritopic + tritopic topology family.…”

Section: Tetratopic + Tritopic Topology Familymentioning

confidence: 99%

“…and triamines by Hong et al (for which crystal structures are available); the resultant molecules showed selectivity for small gases. 68 The range of shapes possible for the Tet 6 Tri 8 topology spans from a rhombic dodecahedron 32 through an octahedron to a cube 68 as shown in Fig. 13.…”

Section: Tetratopic + Tritopic Topology Familymentioning

confidence: 99%

“…Providing an excess of one BB has been known to skew the topological landscape towards alternative products, where not all of the reactive end groups have formed covalent bonds. 32 Building block geometry and rigidity…”

Section: Stoichiometry Of Building Blocksmentioning

confidence: 99%

“…23) to form a Tet 6 Tri 8 molecule, as previously reported by Warmuth and coworkers. 32 We constructed models with the BBs mixed in both a [6 + 8] ratio and in a [2 + 4] ratio; both topologies were observed depending upon whether a 3 aldehyde : 4 amine stoichiometric ratio was used experimentally (resulting in Tet 6 Tri 8 )…”

Section: The Tetratopic + Tritopic Familymentioning

confidence: 99%

“…There are examples of BBs designed to meet the appropriate geometrical requirements for, for example, forming a molecular cube in an [8 + 12] reaction of eight corner units (with angles of ∼90°) and 12 linear struts for the edge, 30,31 or forming a cuboctahedron via molecular panelling of tritopic and tetratopic BBs. 32 More commonly, once a particular polyhedral cage has been made, a family of related polyhedra can be synthesised via small variations in the functionality of one or the other of the BBs. However, even this can fail, for example we reported a change from a cyclohexane diamine to a cyclopentane diamine resulting in a larger [8 + 12] molecule, with an underlying topology of a cube, forming in place of a [4 + 6] molecule.…”

Section: Topological Control?mentioning

confidence: 99%

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Topological landscapes of porous organic cages

et al. 2017

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We define a nomenclature for the classification of porous organic cage molecules, enumerating the 20 most probable topologies, 12 of which have been synthetically realised to date. We then discuss the computational challenges encountered when trying to predict the most likely topological outcomes from dynamic covalent chemistry (DCC) reactions of organic building blocks. This allows us to explore the extent to which comparing the internal energies of possible reaction outcomes is successful in predicting the topology for a series of 10 different building block combinations.

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Section: Tetratopic + Tritopic Topology Familymentioning

confidence: 99%

Section: Tetratopic + Tritopic Topology Familymentioning

confidence: 99%

Section: Stoichiometry Of Building Blocksmentioning

confidence: 99%

Section: The Tetratopic + Tritopic Familymentioning

confidence: 99%

Section: Topological Control?mentioning

confidence: 99%

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Topological landscapes of porous organic cages

et al. 2017

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Self‐Assembly and Self‐Organization

Geer

Shimizu

2012

Supramolecular Chemistry

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From the child making rock candy with his parents to the physicist studying the cosmic dust in deep space, the process of self‐assembly organizes smaller building blocks into larger discrete structures without outside influence. In this chapter, we identify and examine some of the factors that guide, limit, and define these supramolecular structures from the atomic up to the centimeter scale with a focus on molecular building blocks. The concepts herein provide the reader with an introduction to this fast developing field and highlight its important applications.

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Carcerands and Hemicarcerands

Warmuth

2012

Supramolecular Chemistry

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Carcerands and hemicarcerands are spherical, hollow host molecules with inner cavities that are large enough to accommodate smaller organic guest molecules. Since the first synthesis of a carcerand in the mid‐1980s, a large variety of different hemicarcerands and carcerands have been prepared and their properties investigated. In this review, mechanism and scope of (hemi)carcerand synthesis, which is a templated reaction, is discussed. This includes recent work on dynamic hemicarcerands, in which building blocks are connected via dynamic covalent bonds, and gated hemicarcerands, which open and/or close in response to an external trigger such as irradiation or the addition of acid, base, or thiols. In the second part of this chapter, the molecular recognition properties of hemicarcerands are reviewed. As part of this, binding properties of chiral hemicarcerands and water‐soluble hosts are discussed. In the last part, applications of hemicarcerands as molecular reaction flasks are reviewed. Through‐shell reactions between an encapsulated reactant and a bulk‐phase reactant include amine protonation, oxidation/reduction, H/D exchange, and nucleophilic substitutions and additions. In most of these reactions, bond formation/breaking takes place in a size‐restricted portal in the host shell. Thus, scope and reaction rate depend on guest orientation in the inner phase as well as size and shape of the bulk‐phase reactant relative to those of the hemicarcerand's portal. Hemicarcerands have also been used extensively for the inner‐phase stabilization of reactive intermediates. If a reactive intermediate is generated photochemically or thermally in the inner phase of the hemicarcerand, the surrounding host prevents dimerization of the intermediate or reactions with bulk‐phase reactants that cannot pass through an opening in the host shell. Many otherwise fleeting intermediates gain longevity through this extrinsic stabilization, making possible their observation, for example, by NMR spectroscopy. Examples that are discussed include cyclobutadiene, benzyne, anti ‐Bredt olefins, cyclic allenes and ketenimines, carbenes, and nitrenes. Furthermore, investigations of photoelectron transfer and energy transfer across the shell of hemicarcerands have improved our understanding of these important photophysical processes. Recent advances in this area are discussed.

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Multicomponent Dynamic Covalent Assembly of a Rhombicuboctahedral Nanocapsule

Cited by 114 publications

References 73 publications

Topological landscapes of porous organic cages

Topological landscapes of porous organic cages

Self‐Assembly and Self‐Organization

Carcerands and Hemicarcerands

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