April 2012 – Dalton Transactions Blog

Archive for April, 2012

Cryo-TEM reaveals POM-nanoparticle interactions

27 Apr 2012

Ira Weinstock and colleagues from Ben Gurion University of the Negev have used cryogenic transmission electron microscopy to evaluate the interactions of polyoxometallates of different dimensions and shapes with gold nanoparticles. The study revealed a “face-down” orientation of the Pressyler ion [NaP₅W₃₀O₁₁₀]^14–, and a “tilted” orientation for the Finke-Droege ion [P₄W₃₀Zn₄(H₂O)₂O₁₁₂]^16–, contributing to important ongoing studies on the design of functional-POM protected metal nanoparticles.

"Face-down" orientation of Pressyler ion maximises interactions between cluster anion and Au surface.

To read more, download the communication now – it’s free to access.

Orientations of polyoxometalate anions on gold nanoparticles
Shelly Sharet, Ella Sandars, Yifeng Wang, Offer Zeiri, Alevtina Neyman, Louisa Meshi and Ira A. Weinstock
Dalton Trans., 2012
DOI: 10.1039/C2DT30592E

The findings in the above HOT communication are due to be included in an upcoming themed issue on Polyoxometalates, guest edited by Leroy Cronin and Deliang Long.

Yifeng Wang and Ira Weinstock’s previous Dalton Transactions perspective might also be of interest….

Cation mediated self-assembly of inorganic cluster anion building blocks
Yifeng Wang and Ira A Weinstock
Dalton Trans., 2010, 39, 6143-6152
DOI: 10.1039/C0DT00166J

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Delivering cancer-combatting compounds

27 Apr 2012

Scientists from Switzerland have developed a cage-encapsulated ruthenium complex for killing cancer cells.

The multifunctional drug has several features providing it with it’s fantastic anti-cancer properties… 1) it’s ruthenium based instead of platinum (less toxic and has been shown to overcome certain resistance mechanisms induced by Pt); 2) the pyrenyl ligands can easily intercalate with the DNA base pairs; and 3) the metalla-cage bestows water-solubility on the drug therefore enabling it to be internalised within the cancerous cells.

Not only that, the pyrene moiety is fluorescent so the uptake of the drug into the cell can be recorded in action.

Read the HOT article by Bruno Therrien and team now…
Cellular delivery of pyrenyl-arene ruthenium complexes by a water-soluble arene ruthenium metalla-cage
Mona Anca Furrer, Frédéric Schmitt, Michaël Wiederkehr, Lucienne Juillerat-Jeanneret and Bruno Therrien

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Inducing hysteretic spin crossover in solution

23 Apr 2012

Devices that store information magnetically are widespread, from the old floppy disks to credit cards and hard disks. The evolution of computer technologies requires us to continually develop new materials to allow new devices to out-perform their predecessors, for some time molecular spin cross-over complexes have been excellent candidates for new magnetic storage media.

Could mononuclear complexes be the future of magnetic storgae media? Fe3+ organometallic magnetism magnetic storage media

Could mononuclear complexes in solution be the future of magnetic storage media?

This Hot Communication from Grace Morgan and colleagues details their developments in creating an Fe(III) complex which possesses magnetic hysteresis in solution. The authors note that spin cross over in some solid state materials is affected by polymorphism, counter ions and crystallisation solvents in the material. Find out more about the teams discoveries in solution by downloading their article while it is free…

Inducing hysteretic spin crossover in solution
Paulo N. Martinho, Yannick Ortin, Brendan Gildea, Claudio Gandolfi, George McKerr, Barry O’Hagan, Martin Albrecht and Grace G. Morgan
DOI: 10.1039/C2DT12036D

Remeber you can keep up to date with all the latest news in inorganic chemistry by following us on twitter and signing up to our e-alert service.

The following articles might also be of interest;

A magnetic iron(III) switch with controlled and adjustable thermal response for solution processing
Claudio Gandolfi, Grace G. Morgan and Martin Albrecht
DOI: 10.1039/C2DT12037B

Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes
Claudio Gandolfi, Tatiana Cotting, Paulo N. Martinho, Olha Sereda, Antonia Neels, Grace G. Morgan and Martin Albrecht
DOI: 10.1039/C0DT01222J

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A Novel Decanuclear Cobalt(II) Cluster

20 Apr 2012

Polynuclear complexes contain several metal atoms or ions in a single coordination species and therefore their electronic structures and magnetic properties can be quite complex. These properties give polynuclear complexes potential for applications in information storage devices and molecular magnets.

Ruren Xu, Jihong Yu and their team at Jilin University, China have reported the synthesis of a novel cobalt(II) polynuclear complex. This new complex is a decanuclear cobalt (II) cluster with bridging Co₃^2-anions and 8-hydroxyquinoline ligands. Interestingly, the ten cobalts are arranged in an adamantane topology which is a chair-like conformation, The adamantane topology of the cobalt culster can be seen clearly in green in the left hand figure. To the researchers’ knowledge, this is the first example of a metallic skeleton with an adamantane topology in a polynuclear complex. It was also found that an antiferromagentic interaction exists within the complex.

This novel complex is unlike any other cobalt polynuclear complex that has been reported before.

To find out more about the fascinating stucture of this decanuclear cobalt (II) cluster, read the full Dalton Transactions article:

A novel decanuclear Co(II) cluster with adamantane-like metallic skeleton supported by 8-hydroxyquinoline and in situ formed CO₃²⁻ anions
Lei Wang, Yi Li, Yu Peng, Zhiqiang Liang, Jihong Yu and Ruren Xu

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Boranes and Borohydrides themed issue – submissions open

10 Apr 2012

Submissions are now open for the Dalton Transactions themed issue on Boranes and Borohydrides, guest edited by Professor Simon Aldridge (University of Oxford).

Borane and borohydride containing molecules/materials constitute an exciting and rapidly developing field which spans a wide breadth of chemistry, and has seen a number of major fundamental developments in recent years. Applications in fields as diverse as catalysis, organic synthesis, polymer chemistry and functional materials science, sensors, and energy highlight the impact of research currently being carried out.

This Dalton Transactions themed issue will seek to highlight to the inorganic research community the latest and very best research in the field.

We will consider all types of article: Communications, Full Papers, Frontiers and Perspectives (please contact the Editorial Office if you would like to contribute a Frontier or Perspective article). For further information on article types, see our author guidelines. Please note that the normal refereeing procedure will apply and inclusion in the issue is subject to the discretion of the guest editor.

Submission deadline: 20th July 2012

Submit now! We look forward to receiving it shortly…

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Computational investigation suggests symbiotic interaction between borane-phosphine frustrated Lewis pairs and nitrous oxide

05 Apr 2012

Computational studies of complexation of nitrous oxide by borane–phosphine frustrated Lewis pairs Thomas Gilbert from Northern Illinois University reports on a computational study looking at Ar₃B–ONN–PR₃ complexes that result from reactions between borane-phosphine frustrated Lewis pairs and N₂O. By exploring the structure, stability, mechanism of formation and functionalisation of Ar₃B–ONN–PR₃ complexes, we can further understand how frustrated Lewis pairs can capture small molecules, like N₂O, and hold them for derivatisation, in a similar way to enzymes.

A key finding from this study is a symbiotic relationship that forms between Lewis acid and Lewis base to overcome endothermic or weakly exothermic energetics, forming one structural isomer in preference to others. Gilbert makes several other exciting conclusions so download the manuscript whilst it’s free to find out more….

Computational studies of complexation of nitrous oxide by borane–phosphine frustrated Lewis pairs
Thomas M. Gilbert
Dalton Trans., 2012
DOI: 10.1039/C2DT30208J

Frustrated Lewis pairs are compounds or mixtures combining sterically hindered Lewis donors and acceptors. Such systems are capable of unique reactivity with fascinating applications in stoichiometry and catalysis. Dalton Transactions will be publishing a themed issue on frustrated Lewis pairs later in the year – below are some other articles due to be included in the issue:

Exchange chemistry of tBu₃P(CO₂)B(C₆F₅)₂Cl
Rebecca C. Neu, Gabriel Ménard and Douglas W. Stephan
Dalton Trans., 2012
DOI: 10.1039/C2DT30206C

Dimeric aluminum–phosphorus compounds as masked frustrated Lewis pairs for small molecule activation
Steffi Roters, Christian Appelt, Hauke Westenberg, Alexander Hepp, J. Chris Slootweg, Koop Lammertsma and Werner Uhl
Dalton Trans., 2012
DOI: 10.1039/C2DT30080J

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Bimetallic tuneable MOFs – a one-pot wonder

05 Apr 2012

Laurance Beauvais and colleagues have synthesised a mixed metal MOF allowing different divalent metal ions to be easily incorporated into the framework. A bimetallic approach means that one metal can be used for structural integrity, whilst the other can be functional, for application in catalysis for example. The team chose a porprhyrin-based ligand to underpin the framework since this has two distinct metal binding sites – a structural metal binding site at the carboxy and pyridyl ligands; and a functional metal binding site within the porphyrin cavity.

By adding the metals together in a one-pot reaction, the porphyrin framework incorporates both metals with the larger metal ions occupying the structural sites.

With the synthetic method now done and dusted, the team will now look into the catalytic and luminescent properties of these coordination framework materials.

Read Beauvais’ HOT article now… A heterometallic metal-organic framework with tuneable reactive metal sites: synthesis, characterization, and reactivity
Nathan C. Smythe, Derek P. Butler, Curtis E. Moore, William R. McGowan, Arnold L. Rheingold and Laurance G. Beauvais

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Fixing Nitrogen

05 Apr 2012

The well known Haber Bosch process converts nitrogen and hydrogen into ammonia under very harsh reaction conditions. Nitrogen fixation in biology however, takes place at ambient pressure and temperature. A long term goal of researchers has been to achieve nitrogen fixation under ambient conditions.

Whilst molybdenum- and tungsten-dinitrogen complexes containing phosphine ligands are able to reduce nitrogen to ammonia under ambient conditions (in the presence of an acid such as sulfuric acid), these complexes are unable to produce ammonia from molecular dihydrogen.

Yoshiaki Nishibayashi from the University of Tokyo has recently developed a dinitrogen-bridged dimolybdenum complex bearing tridentate PNP pincer ligand which is a diphosphine containing a nitrogen linker. The catalyst is able to produce 23 equivalents of ammonia under atmospheric pressure. A second molybdenum based catalyst, this time bearing ferrocenyl diphosphine ligands is able to produce 226 equivalents of silylamine in the presence of trimethylsilyl chloride and sodium under atmospheric pressure. A future study of the reaction mechanism of these new catalytic systems could provide more insight to guide the design of more effective catalyzed nitrogen fixation in the future.

Nishibayashi has written a comprehensive article that discusses previous work on catalysts for dinitrogen fixation and also reports his recent work on two new nitrogen fixation systems catalyzed by molybdenum-dintrogen complexes. To find out more read the Dalton Transactions Perspective article.

Molybdenum-catalyzed reduction of molecular dinitrogen under mild reaction conditions

Yoshiaki Nishibayashi

Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30105A

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HOT Article: Role of Zn and Mn in Parkinson’s Disease

03 Apr 2012

Model of the YPK9 protein In this HOT article, Zoroddu and coworkers present NMR (mono- and bi-dimensional) and EPR analysis of Zn and Mn complexation to small fragments of the Park9 gene (a member of the P5-type ATPase family) important in Parkinson’s disease (PD). This type of study may provide an insight into the understanding of the connection between genetic and environmental PD causes. The group are planning further investigations, involving the role of the entire protein.

Read more for FREE until 16th April 2012 at:

Mn(II) and Zn(II) interactions with peptide fragments from Parkinson’s disease genes
Serenella Medici, Massimiliano Peana, Lucia Gemma Delogu and Maria Antonietta Zoroddu
Dalton Trans., 2012, 41, 4378-4388
DOI: 10.1039/C2DT12168A

The following critical review may also be of interest:

The potential application of iron chelators for the treatment of neurodegenerative diseases
Robert C. Hider, Sourav Roy, Yong Min Ma, Xiao Le Kong and Jane Preston
Metallomics, 2011, 3, 239-249
DOI: 10.1039/C0MT00087F

You can also keep up to date with the latest news in inorganic chemistry by following us on twitter or signing up to our e-alert service.

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Dalton Transactions Blog

Archive for April, 2012

Cryo-TEM reaveals POM-nanoparticle interactions

Delivering cancer-combatting compounds

Top ten most accessed articles in March

Inducing hysteretic spin crossover in solution

A Novel Decanuclear Cobalt(II) Cluster

Boranes and Borohydrides themed issue – submissions open

Computational investigation suggests symbiotic interaction between borane-phosphine frustrated Lewis pairs and nitrous oxide

Bimetallic tuneable MOFs – a one-pot wonder

Fixing Nitrogen

HOT Article: Role of Zn and Mn in Parkinson’s Disease

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