Design of hydrophobic polyoxometalate hybrid assemblies beyond surfactant encapsulation

Song, Y.-F., McMillan, N., Long, D.-L. , Thiel, J., Ding, Y., Chen, H., Gadegaard, N. and Cronin, L. (2008) Design of hydrophobic polyoxometalate hybrid assemblies beyond surfactant encapsulation. Chemistry: A European Journal, 14(8), pp. 2349-2354. (doi: 10.1002/chem.200701629)

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Grafting of C-6, C-16 and C-18 alkyl chains onto the hydrophilic Mn-Anderson clusters (compounds 24) has been achieved. Exchange of the tetrabutyl ammonium (TBA) with dimethyldioctadecyl ammonium (DMDOA) results in the formation of new polyoxometalate (POM) assemblies (compounds 5-6), in which the POM cores are covalently functionalized by hydrophilic alkyl-chains and enclosed by surfactant of DMDOABr. As a result, we have been able to design and synthesize POM-containing hydrophobic materials beyond surfactant encapsulation. In solid state, scanning electron and transmission electron microscopy (SEM and TEM) studies of the TBA salts of compounds 3 and 4 show highly ordered, uniform, reproducible assemblies with unique segmented rodlike morphology. SEM and TEM studies of the DMDOA salts of compounds 5 and 6 show that they form spherical and sea urchin 3D objects in different solvent systems. In solution, the physical properties of compound 5 and 6 (combination of surfactant-encapsulated cluster (SEC) and surface-grafted cluster (SGC)) show a liquid-to-gel phase transition in pure chloroform below 0 degrees C, which are much lower than other reported SECs. By utilizing light scattering measurements, the nanoparticle size for compounds 5 and 6 were measured at 5 degrees C and 30 degrees C, respectively. Other physical properties including differential scanning calorimetry have been reported

Item Type:Articles
Glasgow Author(s) Enlighten ID:McMillan, Miss Nicola and Thiel, Mr Johannes and Gadegaard, Professor Nikolaj and Long, Dr Deliang and Cronin, Professor Lee
Authors: Song, Y.-F., McMillan, N., Long, D.-L., Thiel, J., Ding, Y., Chen, H., Gadegaard, N., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
College of Science and Engineering > School of Engineering > Biomedical Engineering
Journal Name:Chemistry: A European Journal
Journal Abbr.:Chem. Eur J.
Publisher:Wiley-VCH Verlag
ISSN (Online):1521-3765
Published Online:07 February 2008

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
377311Trapping fundamentally new types of polyoxometalate cluster using a shrink wrapping approachLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)GR/T17205/01Chemistry