Combining analytical and theoretical methods, we present a detailed study of a heteropolytungstate cluster encapsulated in a shell of dendritically branching surfactants, namely (C52H60NO12)(12)(Mn(H2O))(3)(SbW9O33)(2), 3. This novel surfactant-encapsulated cluster (SEC) self-assembles spontaneously from polyoxometalate-containing solutions treated with a stoichiometric amount of dendrons. Compound 3 exhibits a discrete supramolecular architecture in which a single polyoxometalate anion resides in a compact shell of dendrons. Our approach attempts to combine the catalytic activity of polyoxometalates with the steric properties of tailored dendritic surfactants into size-selective catalytic systems. The structural characterization of the SEC is based on analytical ultracentrifugation (AUC) and small-angle neutron scattering (SANS). The packing arrangement of dendrons at the cluster surface is gleaned from molecular dynamics (MD) simulations, which suggests a highly porous shell structure due to the dynamic formation of internal clefts and cavities. From analysis of the MD trajectory of 3, a theoretical neutron-scattering function is derived that is in good agreement with experimental SANS data. Force field parameters used in MD simulations are partially derived from a quantum mechanical geometry optimization of (Zn(H2O))(3)(SbW9O33)(2)(12-), 2b, at the density functional theory (DFT) level. DFT calculations are corroborated by X-ray structure analysis of Na6K6(Zn(H2O))(3)(SbW9O33)(2).23H(2)O, which is isostructural with the catalytically active Mn derivative 2a. The combined use of theoretical and analytical methods aims at rapidly prototyping smart catalysts (''dendrizymes''), which are structurally related to naturally occurring metalloproteins.
%0 Journal Article
%1 Volkmer2002
%A Volkmer, D
%A Bredenkotter, B
%A Tellenbroker, J
%A Kogerler, P
%A Kurth, DG
%A Lehmann, P
%A Schnablegger, H
%A Schwahn, D
%A Piepenbrink, M
%A Krebs, B
%C 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
%D 2002
%I AMER CHEMICAL SOC
%J JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
%K dgkurth
%N 35
%P 10489-10496
%R 10.1021/ja017613b
%T Structure and properties of the dendron-encapsulated polyoxometalate (C52H60NO12)(12)(Mn(H2O))(3)(SbW9O33)(2), a first generation dendrizyme
%U http://dx.doi.org/10.1021/ja017613b
%V 124
%X Combining analytical and theoretical methods, we present a detailed study of a heteropolytungstate cluster encapsulated in a shell of dendritically branching surfactants, namely (C52H60NO12)(12)(Mn(H2O))(3)(SbW9O33)(2), 3. This novel surfactant-encapsulated cluster (SEC) self-assembles spontaneously from polyoxometalate-containing solutions treated with a stoichiometric amount of dendrons. Compound 3 exhibits a discrete supramolecular architecture in which a single polyoxometalate anion resides in a compact shell of dendrons. Our approach attempts to combine the catalytic activity of polyoxometalates with the steric properties of tailored dendritic surfactants into size-selective catalytic systems. The structural characterization of the SEC is based on analytical ultracentrifugation (AUC) and small-angle neutron scattering (SANS). The packing arrangement of dendrons at the cluster surface is gleaned from molecular dynamics (MD) simulations, which suggests a highly porous shell structure due to the dynamic formation of internal clefts and cavities. From analysis of the MD trajectory of 3, a theoretical neutron-scattering function is derived that is in good agreement with experimental SANS data. Force field parameters used in MD simulations are partially derived from a quantum mechanical geometry optimization of (Zn(H2O))(3)(SbW9O33)(2)(12-), 2b, at the density functional theory (DFT) level. DFT calculations are corroborated by X-ray structure analysis of Na6K6(Zn(H2O))(3)(SbW9O33)(2).23H(2)O, which is isostructural with the catalytically active Mn derivative 2a. The combined use of theoretical and analytical methods aims at rapidly prototyping smart catalysts (''dendrizymes''), which are structurally related to naturally occurring metalloproteins.
@article{Volkmer2002,
abstract = {Combining analytical and theoretical methods, we present a detailed study of a heteropolytungstate cluster encapsulated in a shell of dendritically branching surfactants, namely (C52H60NO12)(12){[}(Mn(H2O))(3)(SbW9O33)(2)], 3. This novel surfactant-encapsulated cluster (SEC) self-assembles spontaneously from polyoxometalate-containing solutions treated with a stoichiometric amount of dendrons. Compound 3 exhibits a discrete supramolecular architecture in which a single polyoxometalate anion resides in a compact shell of dendrons. Our approach attempts to combine the catalytic activity of polyoxometalates with the steric properties of tailored dendritic surfactants into size-selective catalytic systems. The structural characterization of the SEC is based on analytical ultracentrifugation (AUC) and small-angle neutron scattering (SANS). The packing arrangement of dendrons at the cluster surface is gleaned from molecular dynamics (MD) simulations, which suggests a highly porous shell structure due to the dynamic formation of internal clefts and cavities. From analysis of the MD trajectory of 3, a theoretical neutron-scattering function is derived that is in good agreement with experimental SANS data. Force field parameters used in MD simulations are partially derived from a quantum mechanical geometry optimization of {[}(Zn(H2O))(3)(SbW9O33)(2)](12-), 2b, at the density functional theory (DFT) level. DFT calculations are corroborated by X-ray structure analysis of Na6K6{[}(Zn(H2O))(3)(SbW9O33)(2)].23H(2)O, which is isostructural with the catalytically active Mn derivative 2a. The combined use of theoretical and analytical methods aims at rapidly prototyping smart catalysts ({''}dendrizymes{''}), which are structurally related to naturally occurring metalloproteins.},
added-at = {2011-01-12T12:45:32.000+0100},
address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA},
affiliation = {Volkmer, D (Reprint Author), Univ Bielefeld, Dept Inorgan Chem 1, POB 100 331, D-33501 Bielefeld, Germany. Univ Bielefeld, Dept Inorgan Chem 1, D-33501 Bielefeld, Germany. Iowa State Univ Sci \& Technol, Dept Phys \& Astron, Ames, IA 50011 USA. Max Planck Inst Colloids \& Interfaces, D-14424 Potsdam, Germany. Univ Hamburg, Inst Chem Phys, D-20146 Hamburg, Germany. Forschungszentrum Julich, Inst Festkorperforsch, IFF, D-52425 Julich, Germany. Univ Munster, Inst Inorgan Chem, D-48149 Munster, Germany.},
author = {Volkmer, D and Bredenkotter, B and Tellenbroker, J and Kogerler, P and Kurth, DG and Lehmann, P and Schnablegger, H and Schwahn, D and Piepenbrink, M and Krebs, B},
author-email = {dirk.volkmer@uni-bielefeld.de kurth@mpikg-golm.mpg.de krebs@uni-muenster.de},
biburl = {https://www.bibsonomy.org/bibtex/2c74f330458c064cfd590f460016a3bdb/lctm},
doc-delivery-number = {591LH},
doi = {10.1021/ja017613b},
interhash = {576f2067269f60aa0c89a9f15862960e},
intrahash = {c74f330458c064cfd590f460016a3bdb},
issn = {0002-7863},
journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
journal-iso = {J. Am. Chem. Soc.},
keywords = {dgkurth},
keywords-plus = {MANGANESE-CONTAINING POLYOXOMETALATE; HYDROGEN-PEROXIDE; HETEROPOLYMETALATE CLUSTERS; ENANTIOSELECTIVE CATALYSIS; DENDRITIC ENCAPSULATION; ENERGY; EPOXIDATION; CHEMISTRY; DENDRIMERS; COMPLEXES},
language = {English},
month = {SEP 4},
number = 35,
number-of-cited-references = {51},
pages = {10489-10496},
publisher = {AMER CHEMICAL SOC},
subject-category = {Chemistry, Multidisciplinary},
times-cited = {58},
timestamp = {2011-01-12T12:45:32.000+0100},
title = {Structure and properties of the dendron-encapsulated polyoxometalate (C52H60NO12)(12){[}(Mn(H2O))(3)(SbW9O33)(2)], a first generation dendrizyme},
type = {Article},
unique-id = {ISI:000177881300046},
url = {http://dx.doi.org/10.1021/ja017613b},
volume = 124,
year = 2002
}