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)]

Kurth DG, Lehmann P, Volkmer D, Müller A, Schwahn D (2000)
Journal of the Chemical Society - Dalton Transactions (21): 3989-3998.

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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.
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Kurth DG, Lehmann P, Volkmer D, Müller A, Schwahn D. 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)]. Journal of the Chemical Society - Dalton Transactions. 2000;(21):3989-3998.
Kurth, D. G., Lehmann, P., Volkmer, D., Müller, A., & Schwahn, D. (2000). 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)]. Journal of the Chemical Society - Dalton Transactions(21), 3989-3998.
Kurth, D. G., Lehmann, P., Volkmer, D., Müller, A., and Schwahn, D. (2000). 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)]. Journal of the Chemical Society - Dalton Transactions, 3989-3998.
Kurth, D.G., et al., 2000. 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)]. Journal of the Chemical Society - Dalton Transactions, (21), p 3989-3998.
D.G. Kurth, et al., “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)]”, Journal of the Chemical Society - Dalton Transactions, 2000, pp. 3989-3998.
Kurth, D.G., Lehmann, P., Volkmer, D., Müller, A., Schwahn, D.: 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)]. Journal of the Chemical Society - Dalton Transactions. 3989-3998 (2000).
Kurth, Dirk G., Lehmann, Pit, Volkmer, Dirk, Müller, Achim, and Schwahn, Dietmar. “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)]”. Journal of the Chemical Society - Dalton Transactions 21 (2000): 3989-3998.
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