Supramolecular Archimedean Cages Assembled with 72 Hydrogen Bonds

Liu, Yuzhou; Hu, Chunhua; Comotti, Angiolina; Ward, Michael D.

doi:10.1126/science.1204369

Cited by 282 publications

(222 citation statements)

References 43 publications

(13 reference statements)

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“…Crystal engineering has enabled synthetic chemists to mimic virus-like discrete polyhedral structures with more than 100 components through supramolecular assembly from predesigned units (6,7). A longstanding challenge, however, is the creation of complex synthetic assemblies composed of small and simple building units that combine to form extremely complex superstructures, reminiscent of proteins (8).…”

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confidence: 99%

Bottom-up construction of a superstructure in a porous uranium-organic crystal

Vermeulen

Malliakas

et al. 2017

Science

305

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Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers-the largest unit cell found to date for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation of colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nanometers and 6.2 nanometers, respectively-ultimately giving rise to the lowest-density MOF reported to date.

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confidence: 99%

Bottom-up construction of a superstructure in a porous uranium-organic crystal

Vermeulen

Malliakas

et al. 2017

Science

305

249

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“…Only a limited number of coordination compounds with a halogen central atom were described, falling mainly to the groups of periodo tungstates or molybdates [29][30][31]. To the best of our knowledge, there are only three examples of coordination compounds where a low valent halogen atom is present in an aggregate bridging, thus more metal centers with minimum number of 'ligands' being six-(Bi10I20) 10+ , (Pb10I20) [32], and (Pb10I24) 4− [33]-mostly on the basis of the topological analysis being considered as Archimedean polyhedra not Platonian solids. These facts and the unusual bonding behavior of the low valent arsenic fragments to the negatively charged iodine atom led us to the idea of a broader inspection of the nature of these interactions.…”

Section: Resultsmentioning

confidence: 99%

The Interplay between Various σ- and π-Hole Interactions of Trigonal Boron and Trigonal Pyramidal Arsenic Triiodides

et al. 2017

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Boron and arsenic triiodides (BI 3 and AsI 3 , respectively) are similar molecules that differ mainly in their geometries. BI 3 is a planar trigonal molecule with D 3h symmetry, while AsI 3 exhibits a trigonal pyramidal shape with C 3v symmetry. Consequently, the As atom of the AsI 3 molecule has three σ-holes, whereas the B atom of the BI 3 molecule has two symmetrical π-holes. Additionally, there are σ-holes on the iodine atoms in the molecules studied. In the first step, we have studied σ-hole and π-hole interactions in the known monocrystals of BI 3 and AsI 3 . Quantum mechanical calculations have revealed that the crystal packing of BI 3 is dominated by π-hole interactions. In the case of AsI 3 , the overall contribution of dihalogen bonding is comparable to that of pnictogen bonding. Additionally, we have prepared the [Na(THF) 6 ] + [I(AsI 3 ) 6 ] − (AsI 3 ) 2 complex, which can be described as the inverse coordination compound where the iodine anion is the center of the aggregate surrounded by six AsI 3 molecules in the close octahedral environment and adjacent two molecules in remote distances. This complex is, besides expected dihalogen and pnictogen bonds, also stabilized by systematically attractive dispersion interactions.

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“…[12,13] Large guests are fully encapsulated within the M 24 L 8 octahedral cavity and are unable to interact with the outside environment, meaning that our results have established astep toward the development of giant synthetic capsules with strong guest encapsulation abilities.…”

Section: Zuschriftenmentioning

confidence: 94%

Capsule–Capsule Conversion by Guest Encapsulation

et al. 2016

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Guest-induced M 18 L 6 -M 24 L 8 capsule-capsule conversion is reported. Both capsules are composed of Pd II ethylenediamine units (M) and 1,3,5-tris(3,5-pyrimidyl)pyrimidine (L), and form trigonal bipyramidal (M 18 L 6 )a nd octahedral (M 24 L 8 )c losed-shell structures with huge hydrophobic inner spaces.T he M 18 L 6 trigonal bipyramid is converted to the M 24 L 8 octahedron through encapsulation of large aromatic guests,w ith the latter capsule possessing ac avity volume three times larger than the former.Despite the dynamic properties of the capsule host, the encapsulated guests are difficult to extract and are thus isolated from the external environment.Molecular capsules show unique host properties that are different from those of other synthetic hosts in that they possess isolated nanocavities that allow the properties and reactivities of encapsulated guests to be maintained.[1] Recently,al ot of effort has been put into constructing capsular structures of ever-increasing size, [2] but relatively few of these capsules show distinct guest-binding properties in their large cavities,t hus demonstrating that simple cavity expansion does not automatically lead to large guest encapsulation. We have previously reported trigonal bipyramidal M 18 L 6 coordination capsule 1a,b ut, unlike similar M 6 L 4 open cages that bind various organic guests in their cavities, [3] capsule 1a did not show any encapsulation behavior toward organic guests in water.[2b] We assumed that, in addition to the open framework, the highly electron-deficient environment of the M 6 L 4 cages offered by the metal-coordinated tris(4-pyridyl)triazine ligand is essential for guest binding.W etherefore redesigned the panel ligand of capsule 1a to give am ore electrondeficient 1,3-pyrimidine-cored panel, and created the more electron-deficient M 18 L 6 capsule 1b.H erein, we report that capsule 1b does indeed encapsulate large guests and, unexpectedly and surprisingly,t he large guest encapsulation triggers the conversion of M 18 L 6 capsule 1b into cavityexpanded M 24 L 8 octahedral capsule 2b (Figure 1). This guesttriggered M 18 L 6 -M 24 L 8 switch presents ar are example of capsule-capsule conversion with concurrent dramatic cavity expansion. [4] By simply mixing [(en)Pd(ONO 2 ) 2 ]( 3;e n= ethylenediamine) and our new ligand 2,4,6-tris(3,5-pyrimidyl)pyrimidine (4)i nw ater, trigonal bipyramidal M 18 L 6 coordination capsule 1b was obtained. Amixture of 3 (34.9 mg, 120 mmol) and 4 (12.6 mg, 40 mmol) was stirred in D 2 Osolution at 70 8 8C for 24 h, and the 1 HNMR spectrum after the complexation clearly showed the formation of as ingle product with panel ligand 4 placed in a C 2v environment. Six aromatic signals were observed in a1:2:2:2:2:1 integral ratio (Figure 2a), thus suggesting that 3 and 4 were assembled into trigonal bipyramid 1b with D 3h symmetry and am irror plane (s h ) vertical to the main apical C 3 axis.T here are many possible isomers of this M 18 L 6 capsular structure because ligand 4 does not have a C 3 symmetr...

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Supramolecular Archimedean Cages Assembled with 72 Hydrogen Bonds

Cited by 282 publications

References 43 publications

Bottom-up construction of a superstructure in a porous uranium-organic crystal

Bottom-up construction of a superstructure in a porous uranium-organic crystal

The Interplay between Various σ- and π-Hole Interactions of Trigonal Boron and Trigonal Pyramidal Arsenic Triiodides

Capsule–Capsule Conversion by Guest Encapsulation

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