Angewandte Chemie International Edition

Cover image for Vol. 45 Issue 29

July 17, 2006

Volume 45, Issue 29

Pages 4699–4873

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
    1. Cover Picture: Enzymatically Derived Sugar-Containing Self-Assembled Organogels with Nanostructured Morphologies (Angew. Chem. Int. Ed. 29/2006) (page 4699)

      George John, Guangyu Zhu, Jun Li and Jonathan S. Dordick

      Version of Record online: 10 JUL 2006 | DOI: 10.1002/anie.200690100

      Enzymatically synthesized symmetrical trehalose diesters self-assemble into fibrous gel networks in a wide range of organic solvents and at very low gelator concentrations. Gels containing acrylate functionalities can be further stabilized through polymerization. In the presence of added water and the same enzyme, the gels degrade into trehalose, as shown in the cover picture. In their Communication on page 4772 ff., J. S. Dordick et al. describe how combining the principles of supramolecular chemistry and the selectivity of biocatalysis represents a powerful strategy to develop defined functional materials.

  2. Graphical Abstracts

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
  3. Meeting Reviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
  4. Book Reviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
  5. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
    1. C3 Symmetry: Molecular Design Inspired by Nature (pages 4718–4720)

      Susan E. Gibson and M. Paola Castaldi

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200600776

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      Symmetry and molecular recognition: The presence of C3 symmetry in nature has recently inspired the first biomimetic C3-symmetric catalyst for asymmetric syntheses (see picture). Threefold symmetry also features in a recent approach to modulating the function of the tumor necrosis factor receptor superfamily.

    2. Can C3-Symmetric Receptors Differentiate Enantiomers? (pages 4721–4723)

      Christina Moberg

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200601214

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      Symmetry and chiral recognition: In contrast to previous arguments, recent reports have demonstrated that C3-symmetric receptors can bind chiral substrates with high enantioselectivity (see picture: H=host, G=(S) or (R)-configured guest; colored spheres represent different-sized substituents).

  6. Essays

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
    1. Kinetics, Thermodynamics, and the Problem of Selectivity: The Maturation of an Idea (pages 4724–4729)

      Jerome A. Berson

      Version of Record online: 21 JUN 2006 | DOI: 10.1002/anie.200600229

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      Why so slow? Why did it take several decades for the concept of selectivity to develop into a fundamental consideration in organic chemistry? The Essay describes the reception by the scientific community in the first half of the 20th century of the principles of kinetic versus thermodynamic control and explains the physical basis of selectivity (see picture: energy diagram for the reaction of pentamethylenefulvene (A) and maleic anhydride (B)).

  7. Reviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
    1. Asymmetric Heterogeneous Catalysis (pages 4732–4762)

      Maja Heitbaum, Frank Glorius and Iris Escher

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200504212

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      Mirror, mirror on the wall, who is the best asymmetric catalyst of all? The field of heterogeneous asymmetric catalysis is multifarious, vibrant, and creates new possibilities. For example, the use of mesoporous solids (see picture) allows selective immobilization in the pores, which results in improved catalytic properties in a number of cases. The most important methods are discussed in the Review.

  8. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
    1. Anisotropic Decoration of Gold Nanoparticles onto Specific Crystal Faces of Organic Single Crystals (pages 4764–4767)

      Yuzo Fujiki, Nami Tokunaga, Seiji Shinkai and Kazuki Sada

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200601470

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      Face to face: The hexagonal {001} or {00equation image} faces of single crystals of L-cystine were selectively decorated by dipping them into a solution of gold nanoparticles (see picture). The selectivity results from an anisotropic molecular packing of L-cystine in the single crystal.

    2. Total Synthesis of (±)-Symbioimine (pages 4767–4771)

      Georgy N. Varseev and Martin E. Maier

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200601418

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      An inside job: A Lewis acid induced intramolecular Diels–Alder (IMDA) reaction is used as the key step in the formation of symbioimine, an iminium alkaloid. The intermediate octahydronaphthalene is obtained from the IMDA reaction, after which extension of the aldehyde to a nitrile, alkylation of the nitrile, and imine formation allows for an efficient route to the target compound (see scheme; TBS=tert-butyldimethylsilyl).

    3. Enzymatically Derived Sugar-Containing Self-Assembled Organogels with Nanostructured Morphologies (pages 4772–4775)

      George John, Guangyu Zhu, Jun Li and Jonathan S. Dordick

      Version of Record online: 8 JUN 2006 | DOI: 10.1002/anie.200600989

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      The long and short of it: A regioselective enzyme-catalyzed acylation of the disaccharide trehalose generated a family of low-molecular-weight gelators with unprecedented properties. The selectivity of enzymatic catalysis enables direct control over gelation properties by simply varying the acyl-chain length to give gelation in solvents ranging from the highly hydrophilic acetonitrile to the highly hydrophobic cyclohexane.

    4. Highly Efficient Aerobic Oxidation of Alcohols Using a Recoverable Catalyst: The Role of Mesoporous Channels of SBA-15 in Stabilizing Palladium Nanoparticles (pages 4776–4779)

      Babak Karimi, Sedigheh Abedi, James H. Clark and Vitaly Budarin

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200504359

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      Scaling down the activity: An efficient recyclable palladium-based catalyst has been developed for the aerobic oxidation of alcohols (see scheme). The combination of a substituted bipyridyl ligand and ordered mesoporous channels (in SBA) causes a synergistic effect that results in enhanced activity, the prevention of agglomeration of the palladium nanoparticles, and the generation of a durable catalyst.

    5. Multiple Length-Scale Patterning of DNA by Stamp-Assisted Deposition (pages 4779–4782)

      Eva Bystrenova, Massimo Facchini, Massimiliano Cavallini, Marcello G. Cacace and Fabio Biscarini

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200600114

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      DNA deposits with submicrometer features can be prepared by micromolding in capillaries on a mica plate (see picture). Upon evaporation, surface properties of the DNA solution and the support come to the fore. The morphology of the DNA deposit can be controlled simply by adjusting the concentrations of the DNA solution and added salt.

    6. Single-Step Conversion of Dimethyl Terephthalate into Cyclohexanedimethanol with Ru5PtSn, a Trimetallic Nanoparticle Catalyst (pages 4782–4785)

      Ana B. Hungria, Robert Raja, Richard D. Adams, Burjor Captain, John Meurig Thomas, Paul A. Midgley, Vladimir Golovko and Brian F. G. Johnson

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200600359

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      Highly active and selective: A supported Ru5PtSn nanoparticle cluster (the picture shows an axial projection of a tomogram), prepared from the carbonyl cluster [PtRu5(CO)15(μ-SnPh2)(μ6-C)], is an excellent catalyst in the single-step hydrogenation of dimethyl terephthalate to cyclohexanedimethanol under mild conditions (100 °C, 20 bar H2).

    7. Formation of Monodisperse (WO3)3 Clusters on TiO2(110) (pages 4786–4789)

      Oleksandr Bondarchuk, Xin Huang, Jooho Kim, Bruce D. Kay, Lai-Sheng Wang, J. M. White and Zdenek Dohnálek

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200600837

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      In groups of three: Monodisperse clusters of WO3 were prepared on a TiO2(110) surface through direct sublimation of WO3 onto the substrate at 300 K followed by annealing to 600 K (see image). Combined evidence from scanning tunneling microscopy, X-ray photoelectron spectroscopy, quartz crystal mass balance, and density functional theory strongly indicates that the clusters are cyclic (WO3)3 species.

    8. Generalized Fabrication of Multifunctional Nanoparticle Assemblies on Silica Spheres (pages 4789–4793)

      Jaeyun Kim, Ji Eun Lee, Jinwoo Lee, Youngjin Jang, Sang-Wook Kim, Kwangjin An, Jung Ho Yu and Taeghwan Hyeon

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200504107

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      Sequential decoration of silica spheres by covalent bonding of magnetite nanoparticles (blue) and attachment of functional nanoparticles of Au, CdSe/ZnS, or Pd (red) afforded multifunctional assemblies exhibiting combinations of magnetism with surface plasmon resonance (Au), luminescence (CdSe/ZnS), and catalytic activity (Pd), respectively.

    9. Visible-Light Photochromism of Bis(ferrocenylethynyl)ethenes Switches Electronic Communication between Ferrocene Sites (pages 4793–4795)

      Ryota Sakamoto, Masaki Murata and Hiroshi Nishihara

      Version of Record online: 26 JUN 2006 | DOI: 10.1002/anie.200601067

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      Communicating better over a long distance: The bis(ferrocenylethynyl)ethene 1 undergoes E[RIGHTWARDS ARROW]Z photoisomerization upon excitation of a charge-transfer band with visible light (546 nm). This structural change leads to a decrease in the “through-bond” mixed-valence interaction between the two ferrocene units.

    10. Chiral Brønsted Acid Catalyzed Enantioselective Aza-Diels–Alder Reaction of Brassard's Diene with Imines (pages 4796–4798)

      Junji Itoh, Kohei Fuchibe and Takahiko Akiyama

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200601345

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      Brønsted, Brassard, Diels, and Alder: Aldimines 1 undergo aza-Diels–Alder reactions with Brassard's diene 2 in the presence of a chiral cyclic phosphate pyridinium salt 4 as a chiral Brønsted acid to give α,β-unsaturated δ-lactams 3 with excellent enantioselectivity.

    11. Discovery of a Family of Isopolyoxotungstates [H4W19O62]6− Encapsulating a {WO6} Moiety within a {W18} Dawson-like Cluster Cage (pages 4798–4803)

      De-Liang Long, Paul Kögerler, Alexis D. C. Parenty, John Fielden and Leroy Cronin

      Version of Record online: 28 JUN 2006 | DOI: 10.1002/anie.200504600

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      Caged up: A family of isopolyoxotungstate clusters of the form [H4W19O62]6− with a cluster cage (blue) identical to that of the Dawson-type heteropolyacids (red) has been discovered. These comprise a single trigonal-prismatic or octahedral {WO6}6− moiety in place of the two heteroanions found in the Dawson structure.

    12. From Single Molecules to Nanoscopically Structured Functional Materials: Au Nanocrystal Growth on TiO2 Nanowires Controlled by Surface-Bound Silicatein (pages 4803–4809)

      Muhammad Nawaz Tahir, Marc Eberhardt, Helen Annal Therese, Ute Kolb, Patrick Theato, Werner E. G. Müller, Heinz-Christoph Schröder and Wolfgang Tremel

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200503770

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      Biofunctionalized ceramic nanowires: A reactive ester polymer has been used to immobilize silicatein, a hydrolytic enzyme involved in the biomineralization of SiO2, on the surface of TiO2 nanowires. The surface-bound protein retains its original hydrolytic properties and also acts as a reductant for AuCl4 in the synthesis of hybrid TiO2/silicatein/Au nanocomposites.

    13. Overcoming the Insolubility of Molybdenum Disulfide Nanoparticles through a High Degree of Sidewall Functionalization Using Polymeric Chelating Ligands (pages 4809–4815)

      Muhammad Nawaz Tahir, Nicole Zink, Marc Eberhardt, Helen A. Therese, Ute Kolb, Patrick Theato and Wolfgang Tremel

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200504211

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      Deck the walls: The principles of coordination chemistry and multidentate ligand design have been used to functionalize the surface of highly inert MoS2 nanoparticles. In this approach the tetradentate nitrilotriacetic acid ligand was coupled either to a fluorescent ligand (for detection) or to a reactive polymer, which serves as an anchor to the sulfide and oxide surfaces of inorganic fullerene/MoS2 and TiO2 nanorods, respectively (see picture).

    14. Biocatalytic Evolution of a Biocatalyst Marker: Towards the Ultrasensitive Detection of Immunocomplexes and DNA Analysis (pages 4815–4819)

      Bella Shlyahovsky, Valeri Pavlov, Lubov Kaganovsky and Itamar Willner

      Version of Record online: 26 JUN 2006 | DOI: 10.1002/anie.200600073

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      Sensitive ELISA: A new enzyme-labeled immunosorbant assay (ELISA) protocol has been developed that makes use of two enzymatic reactions to detect antibody–antigen interactions: 1) the conversion of prothrombin to thrombin by ecarin and 2) the hydrolysis of a nonfluorescent substrate 1 to a fluorescent product 2 by thrombin. The system was used to detect bovine serum albumin, telomerase, and DNA with high sensitivity.

    15. Bioconjugated Ag Nanoparticles and CdTe Nanowires: Metamaterials with Field-Enhanced Light Absorption (pages 4819–4823)

      Jaebeom Lee, Tanveer Javed, Timur Skeini, Alexander O. Govorov, Garnett W. Bryant and Nicholas A. Kotov

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200600356

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      Shiny silver: A superstructure consisting of Ag nanoparticles and CdTe nanowires connected by a streptavidin (SA) and D-biotin (B) affinity pair displays twofold enhancement of the nanowire luminescence. The optical process involved could also be operative in other metamaterials and could serve as a basis for applications in a variety of optoelectronic devices.

    16. Diels–Alder Reactions Are Faster in Water than in Ionic Liquids at Room Temperature (pages 4824–4825)

      Shraeddha Tiwari and Anil Kumar

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200600426

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      Nobody does it better: A comparative study indicates that water, rather than room-temperature ionic liquids (RTILs), is still the solvent of choice for accelerating Diels–Alder reactions. Both the hydrogen-bonding ability and the viscosity of the solvent are thought to play a role.

    17. Reactions of [ZnR2(L)] Complexes with Dioxygen: A New Look at an Old Problem (pages 4826–4829)

      Janusz Lewiński, Witold Śliwiński, Maciej Dranka, Iwona Justyniak and Janusz Lipkowski

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200601001

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      OR or OOR? The oxygenation of ZntBu2 in the presence of donor ligands demonstrates the tendency of zinc dialkyls to undergo oxidation of only one Zn[BOND]C bond under controlled conditions (see scheme). The formation of alkoxide or peroxide species is influenced by the type of donor ligand employed, and these divergent pathways offer a glimpse into the general mechanism of dioxygen activation.

    18. Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N3)5], [Ta(N3)5], [Nb(N3)6], and [Ta(N3)6], and 1:1 Acetonitrile Adducts [Nb(N3)5(CH3CN)] and [Ta(N3)5(CH3CN)] (pages 4830–4835)

      Ralf Haiges, Jerry A. Boatz, Thorsten Schroer, Muhammed Yousufuddin and Karl O. Christe

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200601060

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      Straightened out: The first binary Group 5 azides were prepared by fluorido–azido exchange starting from MF5 (M=Nb, Ta) and characterized by vibrational spectroscopy. The crystal structure of the acetonitrile adduct [Nb(N3)5(CH3CN)] (see picture) provides the first experimental evidence for the existence of linear M-N-N coordination for azido complexes.

    19. Ruthenium-Catalyzed Propargylic Reduction of Propargylic Alcohols with Silanes (pages 4835–4839)

      Yoshiaki Nishibayashi, Akira Shinoda, Yoshihiro Miyake, Hiroshi Matsuzawa and Mitsunobu Sato

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200601181

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      Ru2can do it! Substitution of the OH moiety in propargylic alcohols by hydride proceeds smoothly with triethylsilane by catalysis with the thiolate-bridged diruthenium complex 1 (see scheme; Cp*=η5-C5Me5). This reaction gives the corresponding alkynes in good to high yields with complete selectivity, in contrast to a monoruthenium-catalyzed hydrosilylation of propargylic alcohols with silanes.

    20. Dinuclear Double-Stranded Metallosupramolecular Ruthenium Complexes: Potential Anticancer Drugs (pages 4839–4842)

      Anna C. G. Hotze, Benson M. Kariuki and Michael J. Hannon

      Version of Record online: 27 JUN 2006 | DOI: 10.1002/anie.200601351

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      Just add a twist: Metallosupramolecular architecture design is used to create anti-cancer agents with high activities in human breast cancer cell lines. Three isomers, which comprise a nonhelical metallocyclophane, an unsaturated double helicate, and a new type of double helicate, bridge the fields of metallosupramolecular architecture and anticancer drug design (picture: double-helical trans/cis isomer; red Ru, green Cl).

    21. Asymmetric Total Synthesis of (−)-Merrilactone A: Use of a Bulky Protecting Group as Long-Range Stereocontrolling Element (pages 4843–4848)

      Masayuki Inoue, Takaaki Sato and Masahiro Hirama

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200601358

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      Designer elegance: The transannular aldol reaction of a cyclooctene diketone is the key step in this total synthesis of the natural enantiomer of merrilactone A (see scheme). The configuration of the two stereocenters generated in the formation of the central bicyclo[3.3.0]octane framework of the natural product was established using a specially designed bulky protecting group.

    22. Umpolung Reactivity of Alkenyl Fischer Carbene Complexes, Copper Enolates, and Electrophiles (pages 4848–4850)

      José Barluenga, Abraham Mendoza, Alejandro Diéguez, Félix Rodríguez and Francisco J. Fañanás

      Version of Record online: 23 JUN 2006 | DOI: 10.1002/anie.200601364

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      Copper makes the difference: An umpolung reactivity of Michael acceptors is observed when alkenyl carbene complexes react with copper ketone enolates and electrophiles. This reaction allows the straightforward synthesis of functionalized three-component coupling products in a completely regio- and diastereoselective way.

    23. Selective Excision of C5 from D-Ribose in the Gas Phase by Low-Energy Electrons (0–1 eV): Implications for the Mechanism of DNA Damage (pages 4851–4855)

      Ilko Bald, Janina Kopyra and Eugen Illenberger

      Version of Record online: 3 JUL 2006 | DOI: 10.1002/anie.200600303

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      Attachment of low-energy electrons to D-ribose triggers a series of complex decomposition reactions associated with the loss of neutral water molecules as well as the excision of C-containing units leading to the degradation of the cyclic structure of the sugar. This excision of C-containing neutral fragments involves C5 exclusively. The sugar unit is thought to play a key role in the mechanism of DNA damage by low-energy electrons.

    24. Highly Stereoselective Allylic Alkylations of Peptides (pages 4855–4858)

      Uli Kazmaier, Jan Deska and Anja Watzke

      Version of Record online: 10 JUL 2006 | DOI: 10.1002/anie.200600509

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      Help from the neighbors: Palladium-catalyzed allylic alkylations are extremely suitable for the stereoselective introduction of unsaturated side chains to peptides (see scheme; TFA=trifluoroacetate). The chiral information of the peptide can be used to control the formation of the new stereogenic center. In general, S amino acids induce the formation of R-configured amino acids.

    25. Heterobimetallic Half-Lanthanidocene Clusters: Novel Mixed Tetramethylaluminato/Chloro Coordination (pages 4858–4863)

      H. Martin Dietrich, Oliver Schuster, Karl W. Törnroos and Reiner Anwander

      Version of Record online: 10 JUL 2006 | DOI: 10.1002/anie.200600905

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      Size does matter: When treated with Me2AlCl, highly soluble bis(aluminate) complexes [Cp*Ln(AlMe4)2] (Ln=Y, La, Nd; Cp*=C5Me5) undergo intrinsic alkyl/chloro ligand-exchange reactions to give products of variable Ln nuclearity, depending on the size of the LnIII metal. The reproducible formation of Y2Al2, La6Al4, and Nd5Al heterobimetallic alkyl clusters leads to novel AlMe4 coordination modes (see picture: La6Al4 cluster).

    26. Microwave-Assisted Synthesis of Luminescent LaPO4:Ce,Tb Nanocrystals in Ionic Liquids (pages 4864–4867)

      Gunnar Bühler and Claus Feldmann

      Version of Record online: 10 JUL 2006 | DOI: 10.1002/anie.200600244

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      Illuminating results: A novel microwave-assisted synthesis in ionic liquids produces highly luminescent and dispersible LaPO4:Ce,Tb nanocrystals (see picture: ethanol dispersion of the nanocrystals in daylight (A) and with UV excitation (B)). This preparation method offers the possibility of synthesisindependent surface conditioning of the nanocrystals.

  9. Previews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstracts
    4. Meeting Reviews
    5. Book Reviews
    6. Highlights
    7. Essays
    8. Reviews
    9. Communications
    10. Previews
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