%0 Journal Article %1 Kurth2000d %A Kurth, DG %A Lehmann, P %A Volkmer, D %A Muller, A %A Schwahn, D %C THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD,, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND %D 2000 %I ROYAL SOC CHEMISTRY %J JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS %K dgkurth %N 21 %P 3989-3998 %R 10.1039/b003331f %T Biologically inspired polyoxometalate-surfactant composite materials. Investigations on the structures of discrete, surfactant-encapsulated clusters, monolayers, and Langmuir-Blodgett films of (DODA)(40)(NH4)(2)(H2O)(n)subset of Mo132O372(CH3CO2)(30)(H2O)(72) %X A detailed analysis of the supramolecular architecture of the nanoporous surfactant-encapsulated cluster (SEC) with theempirical formula (DODA)(40)(NH4)(2)(H2O)(n)subset of Mo132O372(CH3CO2)(30)(H2O)(72) 1 (n approximate to 50) is presented. The open framework architecture of the Keplerate cluster is investigated by means of small angle neutron scattering (SANS) in CDCl3 solutions containing discrete SECs. A simplifying core-shell model of 1 is developed, which describes the SEC as a solvent-filled nanocavity, surrounded by two concentric shells (a first polyoxometalate shell of 2.96 nm outer diameter, and a consecutive surfactant shell of 6.18 nm outer diameter, respectively). The model is successfully applied to probe the content of H2O/D2O guest molecules in the Keplerate host. Different surface analytical techniques are applied to characterize the hierarchical structures of monolayers and thin films of 1. Monolayers at the air-water interface are investigated by means of optical ellipsometry and Brewster angle microscopy. Electron density profiles of the monolayers of 1 are gained from synchrotron X-ray reflectance (XRR) measurements that provide further evidence for the supramolecular core-shell architecture of the SEC. Within the spatial resolution limits of these analytical methods, the current data support a monolayer model consisting of hexagonal close-packed arrays of discrete SECs, floating at the air-water interface. Langmuir-Blodgett (LB) transfer of compressed monolayers on to a solid substrate leads to homogeneous multilayers. In the XRR spectra of LB multilayers of 1 multiple Bragg reflections appear, thus indicating an intrinsic tendency of the SECs to adapt a 3-dimensional, highly ordered solid state structure. Considering the huge variety of structurally different polyoxometalates and the possibility to tailor the surfactant shell by means of classic organic synthesis, the self-organization of hierarchically structured thin films and solids based on SECs bears promising perspectives towards the engineering of functional materials.

@article{Kurth2000d, abstract = {A detailed analysis of the supramolecular architecture of the nanoporous surfactant-encapsulated cluster (SEC) with theempirical formula (DODA)(40)(NH4)(2){[}(H2O)(n)subset of Mo132O372(CH3CO2)(30)(H2O)(72)] 1 (n approximate to 50) is presented. The open framework architecture of the Keplerate cluster is investigated by means of small angle neutron scattering (SANS) in CDCl3 solutions containing discrete SECs. A simplifying core-shell model of 1 is developed, which describes the SEC as a solvent-filled nanocavity, surrounded by two concentric shells (a first polyoxometalate shell of 2.96 nm outer diameter, and a consecutive surfactant shell of 6.18 nm outer diameter, respectively). The model is successfully applied to probe the content of H2O/D2O guest molecules in the Keplerate host. Different surface analytical techniques are applied to characterize the hierarchical structures of monolayers and thin films of 1. Monolayers at the air-water interface are investigated by means of optical ellipsometry and Brewster angle microscopy. Electron density profiles of the monolayers of 1 are gained from synchrotron X-ray reflectance (XRR) measurements that provide further evidence for the supramolecular core-shell architecture of the SEC. Within the spatial resolution limits of these analytical methods, the current data support a monolayer model consisting of hexagonal close-packed arrays of discrete SECs, floating at the air-water interface. Langmuir-Blodgett (LB) transfer of compressed monolayers on to a solid substrate leads to homogeneous multilayers. In the XRR spectra of LB multilayers of 1 multiple Bragg reflections appear, thus indicating an intrinsic tendency of the SECs to adapt a 3-dimensional, highly ordered solid state structure. Considering the huge variety of structurally different polyoxometalates and the possibility to tailor the surfactant shell by means of classic organic synthesis, the self-organization of hierarchically structured thin films and solids based on SECs bears promising perspectives towards the engineering of functional materials.}, added-at = {2011-01-12T11:47:20.000+0100}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD,, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, affiliation = {Kurth, DG (Reprint Author), Max Planck Inst Colloids \& Interfaces, D-14424 Potsdam, Germany. Max Planck Inst Colloids \& Interfaces, D-14424 Potsdam, Germany. Univ Bielefeld, Dept Chem, D-33501 Bielefeld, Germany. Forschungszentrum Julich, Inst Festkorperforsch, D-52425 Julich, Germany.}, author = {Kurth, DG and Lehmann, P and Volkmer, D and Muller, A and Schwahn, D}, author-email = {Kurth@mpikg-golm.mpg.de dirk.volkmer@uni-bielefeld.de}, biburl = {https://www.bibsonomy.org/bibtex/255b4c069ed042acf6ab949dfd23df97a/lctm}, doc-delivery-number = {374EA}, doi = {10.1039/b003331f}, interhash = {e217a42deacbea10765c32e9dc76081e}, intrahash = {55b4c069ed042acf6ab949dfd23df97a}, issn = {1470-479X}, journal = {JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS}, journal-iso = {J. Chem. Soc.-Dalton Trans.}, keywords = {dgkurth}, keywords-plus = {MOLYBDENUM OXIDE; KEPLERATE; OCTANE; NANOPARTICLES; REFLECTIVITY; INTERFACES; DENDRIMERS}, language = {English}, number = 21, number-of-cited-references = {48}, pages = {3989-3998}, publisher = {ROYAL SOC CHEMISTRY}, subject-category = {Chemistry, Inorganic \& Nuclear}, times-cited = {92}, timestamp = {2011-01-12T11:47:20.000+0100}, title = {Biologically inspired polyoxometalate-surfactant composite materials. Investigations on the structures of discrete, surfactant-encapsulated clusters, monolayers, and Langmuir-Blodgett films of (DODA)(40)(NH4)(2){[}(H2O)(n)subset of Mo132O372(CH3CO2)(30)(H2O)(72)]}, type = {Article}, unique-id = {ISI:000165330400034}, year = 2000 }