Drawing Small Cations into Highly Charged Porous Nanocontainers Reveals “Water” Assembly and Related Interaction Problems

Müller, Achim; Krickemeyer, Erich; Bögge, Hartmut; Schmidtmann, Marc; Botar, Bogdan; Talismanova, M. O.

doi:10.1002/ange.200351126

Cited by 72 publications

(117 citation statements)

References 25 publications

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“…Similar calculations have been performed on quasione-dimensional pentagon and hexagon ice nanotubes (H 2 O) 30 , (H 2 O) 60 , and (H 2 O) 120 by Bai et al [13] Related water assemblies (H 2 O) 40 , (H 2 O) 80 , and (H 2 O) 100 were found experimentally in microporous networks or in supramolecular compounds. [14,15] But these cagelike clusters have different numbers of vertices and edges than our carbonanalogue water structures. Additionally, interactions with nanoscaled cavities lead to structural motifs such as trimers, which do not occur in pure water cages.…”

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Calculation of Clathrate‐Like Water Clusters Including H₂O‐Buckminsterfullerene

Ludwig

Appelhagen

2005

Angew Chem Int Ed

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The concept of buckminsterfullerene-like topology as a molecular-level structural motif has a long history in water cluster chemistry.[1] While carbon-based analogues have a well-established experimental foundation, "bucky-water" clusters remain largely conjectural species in the theoretical descriptions of pure water. Fullerene-like topologies are distinguished by the pattern of tricoordinate vertices in pentagonal and hexagonal facets that close to a convex polyhedron in three dimensions. They require exactly 12 pentagons and any number n hex of hexagons to form a polyhedron of 2n hex + 20 vertices. While pentagonal and hexagonal facets are well-known structural elements of all known crystalline forms of ice, [2] the intact Bucky-water polyhedra are principally recognized as elements in certain clathrate-type hydrates, such as the pentagonal dodecahedral (H 2 O) 20 (n hex = 0) and tetrakaidecahedral (H 2 O) 24 units (n hex = 2) of chlorine hydrate. [3] Today, gas hydrates are among the most well-known clathrate structures. These nonstoichiometric, crystalline compounds are found in natural-gas pipelines, on the ocean floor, and in permafrost environments, [4,5] deep ice cores, [6] rock inclusions, [7] comets, and certain outer planets. [8] There are three known types of natural-gas hydrates: the two cubic structures I and II, [9] and a hexagonal structure H.[ Recently, we extended a quantum statistical model of liquid water to include larger ice-like clusters, such as tetrahedral and fullerene-like clusters with up to 26 water molecules.[11] A low-energy tetrakaidecahedral (H 2 O) 24 cluster leads to a new low-temperature phase that bounds both liquid and vapor regions in first-order transition lines and gives rise to a true triple point. We characterized the microstructural composition and macroscopic properties of this "Bucky-ice" phase. Although it differs significantly from physical ice I h (for example, the melting point is 20 K too high and the molar volume is 5 % too low), it manifests qualitatively correct thermodynamic features of true ice polymorphs, which suggests an important role of voluminous clusters in the liquid/solid transition region. Thus understanding the structure and stability of such water clusters is of crucial importance for studying clathrate hydrates and hydration phenomena.The aim of this work is to investigate properties of larger water clusters including up to 60 water molecules. Some key questions will be addressed: Which of the calculated water clusters present minimum structures? How important are cooperative effects with increasing cluster size? Can hydrophobic guest molecules promote structure formation? Are larger clathrate structures than those known experimentally reasonable based on energetic considerations?The calculated bucky-water clusters having between 20 and 60 water molecules are shown in Figure 1. The variety of water cage structures comprises the dodecahedral (H 2 O) 20 cluster (n hex = 0), the tetrakaidecahedral (H 2 O) 24 cluster (n hex = 2), the hexakaidecahed...

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Calculation of Clathrate‐Like Water Clusters Including H₂O‐Buckminsterfullerene

Ludwig

Appelhagen

2005

Angew Chem Int Ed

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“…[4] nÀ , [1,2] the overall charges and internal surfaces of which can be fine-tuned by changing the ligands, thus allowing the type and structure of encapsulates to be influenced. [4] Most important, the 20 {Mo 9 O 9 }-type pores have crown-ether-like function and can be opened and closed with noncovalently bonded guests in a supramolecular fashion.…”

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Porous Capsules Allow Pore Opening and Closing That Results in Cation Uptake

et al. 2005

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“…Die zumeist hoch symmetrischen Kapseln bestehen hierbei aus einzelnen Metall-Ligand-Komponenten, die sich schnell und in hoher Ausbeute zu einer einzigen Spezies, manchmal in der Größenordnung eines Proteins, zusammenlagern können. [1] Das Interesse an diesen Systemen geht weit über den rein ästhetischen Aspekt hinaus, und mit einem tiefgreifenden Verständnis der Aggregationsprozesse sollte es möglich sein, Systeme mit bisher unbekannten physikalischen Eigenschaften und Funktionen zu entwerfen. Vor diesem Hintergrund wurden bereits Käfige entwickelt, die als supramolekulare Nanocontainer, Nanoreaktoren und Modelle [3] Die Bildung von "molekularem Eis" im Hohlraum von Käfigen wie 1 (wobei zehn Wassermoleküle eingeschlossen werden) kann entscheidende Hinweise auf die Reaktivität und WirtGast-Chemie solcher Kapseln geben.…”

Section: Der Aufbau Von Nanometergroßenunclassified

Anorganische molekulare Kapseln: von der Struktur zur Funktion

Cronin

2006

Angewandte Chemie

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Drawing Small Cations into Highly Charged Porous Nanocontainers Reveals “Water” Assembly and Related Interaction Problems

Cited by 72 publications

References 25 publications

Calculation of Clathrate‐Like Water Clusters Including H₂O‐Buckminsterfullerene

Calculation of Clathrate‐Like Water Clusters Including H₂O‐Buckminsterfullerene

Porous Capsules Allow Pore Opening and Closing That Results in Cation Uptake

Anorganische molekulare Kapseln: von der Struktur zur Funktion

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Drawing Small Cations into Highly Charged Porous Nanocontainers Reveals “Water” Assembly and Related Interaction Problems

Cited by 72 publications

References 25 publications

Calculation of Clathrate‐Like Water Clusters Including H2O‐Buckminsterfullerene

Calculation of Clathrate‐Like Water Clusters Including H2O‐Buckminsterfullerene

Porous Capsules Allow Pore Opening and Closing That Results in Cation Uptake

Anorganische molekulare Kapseln: von der Struktur zur Funktion

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Calculation of Clathrate‐Like Water Clusters Including H₂O‐Buckminsterfullerene

Calculation of Clathrate‐Like Water Clusters Including H₂O‐Buckminsterfullerene