Can Hydrophobic Interactions Influence Supramolecular Aggregation in Self-Assembled Organic-Inorganic Hybrid Structures?
- Publication type:
- Journal article
- Metadata:
-
- Autoren
- Kirsten Heussner
- Mathias Grabau
- Johannes Forster
- Carsten Streb
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000297017000007&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1002/ejic.201100676
- eISSN
- 1099-0682
- Externe Identifier
- Clarivate Analytics Document Solution ID: 848AA
- ISSN
- 1434-1948
- Ausgabe der Veröffentlichung
- 33
- Zeitschrift
- EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
- Schlüsselwörter
- Supramolecular chemistry
- Aggregation
- Crystal engineering
- Poly-oxometalates
- Organic-inorganic hybrid composites
- Amphiphiles
- Hirshfeld analysis
- Paginierung
- 5125 - 5131
- Datum der Veröffentlichung
- 2011
- Status
- Published
- Titel
- Can Hydrophobic Interactions Influence Supramolecular Aggregation in Self-Assembled Organic-Inorganic Hybrid Structures?
- Sub types
- Article
Data source: Web of Science (Lite)
- Other metadata sources:
-
- Abstract
- <jats:title>Abstract</jats:title><jats:p>This study aims to provide insights into the ability of amphiphilic cations to influence the assembly of hybrid organic‐inorganic crystal lattices using hydrophobic interactions. To investigate the hypothesis, a prototype amphiphilic cation, <jats:italic>tert</jats:italic>‐butyldiethanolammonium, was employed together with molybdenum oxide clusters of increasing size and charge in the self‐assembly of type I hybrid systems. The molybdate clusters were used as model inorganic building blocks as they can be formed in situ and their size and charge can be adjusted by pH control. Using this strategy, three hybrid structures were obtained and characterized using single‐crystal X‐ray diffraction, theoretical bond valence sum calculations, elemental analysis, FTIR spectroscopy, thermogravimetry and theoretical Hirshfeld analysis. Heptamolybdate Na<jats:sub>5</jats:sub>[<jats:italic>t</jats:italic>BuNH(C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>OH)<jats:sub>2</jats:sub>][Mo<jats:sub>7</jats:sub>O<jats:sub>24</jats:sub>]<jats:bold>·</jats:bold>ca. 14H<jats:sub>2</jats:sub>O (<jats:bold>1</jats:bold>) was isolated, which features sodium‐linked dimeric cluster species. Inaddition, octamolybdate [<jats:italic>t</jats:italic>BuNH(C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>OH)<jats:sub>2</jats:sub>]<jats:sub>4</jats:sub>[Mo<jats:sub>8</jats:sub>O<jats:sub>26</jats:sub>]<jats:bold>·</jats:bold>ca. 4H<jats:sub>2</jats:sub>O (<jats:bold>2</jats:bold>) was isolated, which incorporates a complex cationic sodium network that contains isolated octadecanuclear sodium clusters. At low pH levels (below pH 2),[<jats:italic>t</jats:italic>BuNH(C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>OH)<jats:sub>2</jats:sub>]<jats:sub>14</jats:sub>[Mo<jats:sub>36</jats:sub>O<jats:sub>112</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>16</jats:sub>][Mo<jats:sub>36</jats:sub>O<jats:sub>112</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>14</jats:sub>{<jats:italic>t</jats:italic>BuNH(C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>OH)<jats:sub>2</jats:sub>}<jats:sub>2</jats:sub>]<jats:bold>·</jats:bold>ca. 36H<jats:sub>2</jats:sub>O (<jats:bold>3</jats:bold>) was obtained, which is based on a 36‐centre molybdenum oxide cluster. Crystallographic analysis of the assemblies showed that the formation of hydrophobic regions within the crystal lattice is affected by the size of the inorganic building blocks employed. In <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold>, the hydrophobic <jats:italic>tert</jats:italic>‐butyl groups of the amphiphilic cations aggregate into hydrophobic assemblies. In contrast, the structural arrangement in <jats:bold>3</jats:bold> is dominated by the large inorganic cluster and the organic cations are incorporated as isolated units. This behaviour is further supported by theoretical Hirshfeld surface analysis of the organic counterions, which suggests that, with increasing cluster size, the contribution of long‐range, hydrophobic intermolecular interactions decreases, which is in line with the crystallographic analysis for <jats:bold>1</jats:bold>–<jats:bold>3</jats:bold>.</jats:p>
- Autoren
- Kirsten Heussner
- Mathias Grabau
- Johannes Forster
- Carsten Streb
- DOI
- 10.1002/ejic.201100676
- eISSN
- 1099-0682
- ISSN
- 1434-1948
- Ausgabe der Veröffentlichung
- 33
- Zeitschrift
- European Journal of Inorganic Chemistry
- Sprache
- en
- Online publication date
- 2011
- Paginierung
- 5125 - 5131
- Datum der Veröffentlichung
- 2011
- Status
- Published
- Herausgeber
- Wiley
- Herausgeber URL
- http://dx.doi.org/10.1002/ejic.201100676
- Datum der Datenerfassung
- 2023
- Titel
- Can Hydrophobic Interactions Influence Supramolecular Aggregation in Self‐Assembled Organic–Inorganic Hybrid Structures?
- Ausgabe der Zeitschrift
- 2011
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