Supramolecular Encapsulation of Tetrahedrally Hydrated Guests in a Tetrahedron Host

Wang, Qi‐Qiang; Day, Victor W.; Bowman‐James, Kristin

doi:10.1002/ange.201106090

Cited by 25 publications

(4 citation statements)

References 100 publications

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“…However, a structure containing water clusters was obtained only in the former case, while the remaining ones gave simple monohydrate . Interestingly, a similar observation was reported by Bowman-James in the studies of structurally related cryptands. , This indicates that highly solvated anionic species may participate in the formation of water clusters, which is currently underway in our laboratory. Nevertheless, in Figure a we present the discrete water octamer trapped by tailored H-bonds which are supported by dispersion interactions originating from a matrix formed by eight molecules of UC 1 , as shown in Figure b.…”

supporting

confidence: 85%

Trapping of Octameric Water Cluster by the Neutral Unclosed Cryptand Environment

Dąbrowa

Ceborska

Jurczak

2014

Crystal Growth & Design

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Unclosed cryptands (UCs) are neutral and easily accessible compounds with precisely defined spatial arrangement of various functional groups. They readily form crystals with a unusually high packing efficiency (≥0.8), thus providing a well-suited 3Dframework for study of supramolecular assemblies. Herein, one example of the discrete eight-membered water cluster trapped in the matrix of UC 1 is presented. X-ray, ATR FT-IR, and DFT studies indicate extraordinary stability of this assembly, which originated from the cumulative interplay of many noncovalent interactionshydrogen bonds and London dispersion forces.

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supporting

confidence: 85%

Trapping of Octameric Water Cluster by the Neutral Unclosed Cryptand Environment

Dąbrowa

Ceborska

Jurczak

2014

Crystal Growth & Design

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“…The ligands TREN-MAM (1), 63 TREN-1,2-HOPO (2), 70 TREN-HMA (3), 63,71 and TREN-CMPO-OEt (5) 72 were each synthesized according to literature procedures. TREN-HPA (4) was prepared by analogy of a reported procedure 73 via direct amide coupling of esters and amines according to Scheme 1. Each corresponding Gd III complex (1−5, Figure 1) was then synthesized from their respective ligand and GdCl 3 • 6H 2 O salt in aqueous methanol mixture under slightly basic conditions.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

The Stability of the Complex and the Basicity of the Anion Impact the Selectivity and Affinity of Tripodal Gadolinium Complexes for Anions

et al. 2019

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The affinities and selectivities of lanthanide complexes with open coordination sites for anions vary considerably with the chelate. In order to determine the effect of the stability of a lanthanide complex on its affinity for anions, five different complexes featuring different bidentate chelating moieties were synthesized, and their affinity for anions in water at neutral pH were evaluated by longitudinal relaxometry measurements. The chelates comprise both oxygen and nitrogen donors including maltol, 1,2-hydroxypyridinone, hydroxamic acid, pyridin-2-ylmethanol, and carbamoylmethylphosphonate diester. They were chosen to span a range of basicities all the while maintaining a similar tripodal tris-bidentate architecture, thereby allowing for a direct study of the role of the coordinating motif on the supramolecular recognition of anions by the corresponding Gd III complex. Overall, for ligands containing the same number of protonation steps, and therefore the same charge at neutral pH, the lower the acidity of the chelate (higher ∑pK a 's), the less stable the corresponding Gd III complex, and the higher its affinity for anions. Regardless of the number of protonation steps, the more stable Gd III complexes form ternary or quaternary assemblies with coordinating anions. In contrast, the same anions readily displace the chelate of the least stable complexes, resulting instead in the formation of Gd III •anion precipitates. Irrespective of the chelate, in the absence of steric hindrance at the open coordination site, the affinity of Gd III complexes for anions follows the order phosphate > arsenate > bicarbonate > fluoride. Hence, the selectivity and affinity of Gd III complexes of tripodal tris-bidentate chelates for anions is a function of the stability of the Gd III complex and the basicity of the anion.

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“…Organic hydrates remain an important group of compounds and have been intensively studied. − Such studies are necessary especially for active materials in the pharmaceutical and advanced chemical industries, where incorporation of water molecules into a crystalline lattice can lead to drastically different physical properties of a given crystalline phase. Organic hydrates are also of interest since water molecules very often aid the formation supramolecular structures in a crystal lattice giving insight into water cluster formation, important, for example, in condensation phenomena, atmospheric chemistry, cloud and ice formation, and biochemical processes. − …”

Section: Introductionmentioning

confidence: 99%

Discrete Cuboidal 15- and 16-Membered Water Clusters in Brucine 3.86-Hydrate, Water Release and Its Consequences

Białońska

Ciunik

Ilczyszyn

et al. 2014

Crystal Growth & Design

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Up to now, three brucine hydrates are known, brucine di-, tetra-, and 5.25-hydrate. All of them were obtained from solutions containing the additive diethanolamine, adenosine, and urea, respectively. Studying the role of the additives on crystallization of the brucine hydrates, we obtained a new, kinetically favored brucine 3.86-hydrate. In crystals of brucine 3.86-hydrate, large 15- and 16-membered water clusters of cuboidal topology are encapsulated in cages formed between honeycomb-like brucine layers. Dehydration of the brucine hydrate leads to formation of the known anhydrous brucine, giving insight into a mechanism of the dehydration process, in which a shift of brucine ribbons in the honeycomb-like layers leads to an openining of channels and water release. A collapse of brucine layers after the water release results in formation of the common anhydrous brucine. The anhydrous brucine undergoes a phase transition at 249 K in the cooling mode and at 277 K in the heating mode. The phase transition is attributable to a huge shift of brucine corrugated layers in relation to each other. The phase transition for anhydrous brucine obtained by dehydration is accompanied by thermal effects one order larger than anhydrous brucine, obtained by crystallization from acetone solution.

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Supramolecular Encapsulation of Tetrahedrally Hydrated Guests in a Tetrahedron Host

Cited by 25 publications

References 100 publications

Trapping of Octameric Water Cluster by the Neutral Unclosed Cryptand Environment

Trapping of Octameric Water Cluster by the Neutral Unclosed Cryptand Environment

The Stability of the Complex and the Basicity of the Anion Impact the Selectivity and Affinity of Tripodal Gadolinium Complexes for Anions

Discrete Cuboidal 15- and 16-Membered Water Clusters in Brucine 3.86-Hydrate, Water Release and Its Consequences

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