Archive for the ‘Hot Articles’ Category

Hybrid polyoxometalate

Trapping {BW12}2 tungstoborateKorenev and colleagues present a new hybrid polyoxometalate in this HOT Dalton Transactions Communication. 

The search is on to enhance the structural diversity of POMs and one approach to this is to “hybridise” — a POM structure can be designed to also include a stable polynuclear unit. Several POM structures containing oxothiocations have been synthesised with this in mind, yielding structures with both hard and soft coordination centres.

Korenev and team have used this approach to synthesis a unique architecture that consists of two tungstoborate subunits which are linked with a hexamolybdate “handle” (shown in pink).

To find out more, you can download the Communication now – which is free to access for 4 weeks!

Trapping {BW12}2 tungstoborate: synthesis and crystal structure of hybrid [{(H2BW12O42)2O}{Mo6O6S6(OH)4(H2O)2}]14− anion
V. S. Korenev, P. A. Abramov, C. Vicent, D. A. Mainichev, S. Floquet, E. Cadot, M. N. Sokolov and V. P. Fedin
Dalton Trans., 2012
DOI: 10.1039/C2DT31512B, Communication

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From double-decker to quintuple-decker: single-molecule magnetic behaviour and f-f interactions

This Hot Article from Masahiro Yamashita and Keiichi Katoh investigates the interactions among the 4f electrons of some multiple-decker Tb3+ and Dy3+ complexes, revealing the importance of molecular symmetry and coordination geometry.

Multiple-decker phthalocyaninato dinuclear lanthanoid(III) single-molecule magnets with dual-magnetic relaxation processes

Correlation between the χM′′(T) peak blocking temperature and the distance between the two Tb(III) ions

Single molecule magnets (SMMs) exhibit superparamagnetism at the molecular scale and have potential application in quantum computing, information storage and magnetic refrigeration. Understanding the relationship between the local environment of complexes and their magnetic properties is important to develop new SMMs with desirable magnetic relaxation behaviours.

Download the paper to see the full details of the team’s discoveries

Multiple-decker phthalocyaninato dinuclear lanthanoid(III) single-molecule magnets with dual-magnetic relaxation processes
Keiichi Katoh, Yoji Horii, Nobuhiro Yasuda, Wolfgang Wernsdorfer, Koshiro Toriumi, Brian K. Breedlove and Masahiro Yamashita

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Inspiring inorganic chemists to make their mark in medicine

Declan Gaynor and Darren Griffith discuss how medicinal inorganic chemistry is currently flourishing in this Dalton Transactions Perspective.  Understanding the role of metals in biological systems is very important for drug design; the predictability and control of inorganic complexes make fine-tuning the properties of drugs incorporating such complexes a real possibility.  Metal-based compounds are already routinely administered on a regular basis and this Perspective encourages chemists to further investigate inorganic therapeutic and diagnostic medicine by looking at previous successes, e.g. MRI contrast agents, then moving onto current challenges such as antibacterial compounds for tackling hospital acquired infections.Key areas of applied medicinal inorganic chemistryKey areas of applied medicinal inorganic chemistry

To find out more, you can download the Perspective now – which is free to access for 4 weeks!

The prevalence of metal-based drugs as therapeutic or diagnostic agents: beyond platinum
Declan Gaynor and Darren M. Griffith
Dalton Trans., 2012
DOI: 10.1039/C2DT31601C, Perspective

Also of interest…

Mn(II) complexes of novel hexadentate AAZTA-like chelators: a solution thermodynamics and relaxometric study
Lorenzo Tei, Giuseppe Gugliotta, Marianna Fekete, Ferenc K. Kálmán and Mauro Botta
Dalton Trans., 2011, 40, 2025-2032
DOI: 10.1039/C0DT01114B, Paper

Metallic radionuclides in the development of diagnostic and therapeutic radiopharmaceuticals
Sibaprasad Bhattacharyya and Manish Dixit
Dalton Trans., 2011, 40, 6112-6128
DOI: 10.1039/C1DT10379B, Perspective
From themed issue Radiopharmaceuticals for imaging and therapy

The status of platinum anticancer drugs in the clinic and in clinical trials
Nial J. Wheate, Shonagh Walker, Gemma E. Craig and Rabbab Oun
Dalton Trans., 2010, 39, 8113-8127
DOI: 10.1039/C0DT00292E, Perspective

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Stronger crystal field interactions give actinides advantage over lanthanides in single-molecule magnet construction at high temperatures.

Slow magnetic relaxation in homoleptic trispyrazolylborate complexes of neodymium(III) and uranium(III)Jeffrey Rinehart and Jeffrey Long compare the dynamic properties of the 4f3 complex, NdTp3 (Tp = trispyrazolylborate), and its isostructural 5f3 congener, UTp3. This is the first direct comparison of slow magnetic relaxation behaviour for isostructural and valence isoelectronic lanthanide and actinide complexes.

Download the manuscript which is free to access for 4 weeks to find out more.

Slow magnetic relaxation in homoleptic trispyrazolylborate complexes of neodymium(III) and uranium(III)
Jeffrey D. Rinehart and Jeffrey R. Long
Dalton Trans., 2012
DOI: 10.1039/C2DT31352A, Communication

This manuscript is part of a themed issue titled Frontier and Perspectives in Molecule-Based Quantum Magnets which is due to be published later in the year. Below is a selection of papers also due to be included in this themed issue:

Single-ion magnet behaviour in [U(TpMe2)2I]
Joana T. Coutinho,  Maria A. Antunes,  Laura C. J. Pereira,  Hélène Bolvin,  Joaquim Marçalo,  Marinella Mazzanti and Manuel Almeida
Dalton Trans., 2012
DOI: 10.1039/C2DT31421E, Communication

Controlling magnetic communication through aromatic bridges by variation in torsion angle
Thomas B. Faust,  Floriana Tuna,  Grigore A. Timco,  Marco Affronte,  Valerio Bellini,  Wolfgang Wernsdorfer and Richard E. P. Winpenny
Dalton Trans., 2012
DOI: 10.1039/C2DT31292A, Paper

A oximato-bridged linear trinuclear [MnIVMnIIIMnIV] single-molecule magnet
Chang-Long Zhou,  Zhe-Ming Wang,  Bing-Wu Wang and Song Gao
Dalton Trans., 2012
DOI: 10.1039/C2DT31039B, Paper

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Ball milling oxides

Mechanochemistry has been used for centuries – according to some, as early as 371 B.C. The pestle and mortar still has a place in many chemistry labs but nowadays mechanically-induced chemistry is  performed with the help of a high-energy ball mill.

In their latest Dalton Transactions Perspective, Vladimir Šepelák, Sylvie Bégin-Colin and Gérard Le Caër describe how ball milling is used to effect transformations in oxides. Whilst understanding of the mechanochemical processes involved in ball-milling metalllic compounds is growing, for the more-complex oxide materials, the field is still relatively immature.

The authors explain the various uses of ball milling oxides which can be grouped into either homogeneous or heterogeneous processes (determined by whether there is a net exchange of atoms across boundaries or not). Homogeneous processes encompass polymorphic transformations and titania phase transformations; heterogeneous processes involve compound formations, decompositions and redox reactions.

To read more about the interesting nanocrystalline characteristics that ball milling offers, read the Perspective article now.

Transformations in oxides induced by high-energy ball-milling
Vladimir Šepelák, Sylvie Bégin-Colin and Gérard Le Caër

Interested in other mechanochemistry articles? Read the growing number of articles being added to the ChemComm web theme in mechanochemistry – guest edited by Stuart James and Tomislav Friščić.

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A solid solution for MOF stabilisation

Research in metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) has exploded lately due to their potential applications in diverse areas from gas storage to drug delivery, but the Kitagawa group has been looking at yet another application that has rarely been considered: proton conductivity.  This process would work in a similar way to Nafion, a DuPont product produced since the 1960s in which protons on SO3H groups hop between acid sites that extend from a Teflon backbone.  Modified Nafion’s excellent mechanical and thermal stability allow it to be used as a proton conductor for proton exchange membrane (PEM) fuel cells.

Foo et al. have synthesised a framework containing sulphonic acid groups, where sodium cations were exchanged in situ for protons.  The resultant framework proved to be unstable to loss of guest molecules and, as such, its use in most future applications is limited.

However, through a solid solution approach, where a mixture of ligands was used in differing proportions, mixed MOFs were produced.  The stand-out product was a framework in which 18% of the linkers contained sulphonic acid groups, which retained crystallinity and porosity following evacuation of guest molecules.  The incorporation of this small proportion of acidic groups increased both the total uptake and the heat of adsorption of CO2 at 288 K.

Read about a solid solution approach as an alternative route to stabilising MOFs in this HOT article.

Ligand-based solid solution approach to stabilisation of sulphonic acid groups in porous coordination polymer Zr6O4(OH)4(BDC)6 (UiO-66)
Maw Lin Foo, Satoshi Horike, Tomohiro Fukushima, Yuh Hijikata, Yoshiki Kubota, Masaki Takata and Susumu Kitagawa

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Sulfur oxygenation at non-heme iron centers

McQuilken and Goldberg discuss the synthesis, structure and reactivity of non-heme iron(II/III)-thiolate model complexes that are known to react with O2 to give sulfur oxygenates in this hot Perspective.  Comprehension of the pathways involved in sulfur oxygenation will aid research towards catalytic applications involving metal-mediated O2 oxidations as well as developing understanding surrounding nonheme iron enzymes, many of which are vital of important biochemical pathways.

To find out more, read the full Dalton Transactions Perspective now…

Sulfur oxygenation in biomimetic non-heme iron–thiolate complexes
Alison C. McQuilken and David P. Goldberg
Dalton Trans., 2012
DOI: 10.1039/C2DT30806A, Perspective

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Ambient hydrogen activation by frustrated aminoboranes

Almost ten years ago, Piers et al. described how frustrated aminoboranes could be used to activate molecular hydrogen by exploiting their frustrated Lewis pairs.  Unfortunately the ansa-aminoborane they investigated proved incapable of activating H2, and so this contribution was very much overlooked in the ongoing search for facile H2 activation.

ansa-aminoborane 3A frustrated Lewis pair, in this case, is a molecule that contains a Lewis acid group and a Lewis base group kept apart due to sterics.  Such compounds are, perhaps unsurprisingly, very reactive.  The most important practical application of FLPs is most likely to be the catalysed hydrogenation of polar double bonds under ambient conditions.

The Repo group at the University of Helsinki describe how they have overcome the problems encountered in 2003 to produce two new ansa-aminoboranes which are both capable of activating molecular hydrogen under ambient conditions.  One of their new compounds even shows selective reversible H2 activation at room temperature, providing exciting new developments for FLP catalysis.

Read more about these new catalysts, including why they outperform their predecessors, in this HOT article.

Hydrogen activation by 2-boryl-N,N-dialkylanilines: a revision of Piers’ ansa-aminoborane
Konstantin Chernichenko, Martin Nieger, Markku Leskelä and Timo Repo

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Extracting nuclear energy from seawater

It’s estimated that there’s more than 4.5 billion tons of uranium in the ocean

It’s estimated that there’s more than 4.5 billion tons of uranium in the ocean

US scientists have used a ligand that can form a complex with a uranyl ion to enable uranium to be extracted from seawater. The concentration of uranium in seawater is low at 3.3 parts per billion, but in the vast oceans, it’s estimated that there’s more than 4.5 billion tons of uranium; considerably more than the amount of uranium in terrestrial ores, say the researchers.

Extracting uranium from the sea is a challenge because it exists as a stable carbonate complex. Linfeng Rao from the Lawrence Berkeley National Laboratory, and colleagues, say that a cyclic imide dioxime ligand – glutarimidedioxime – can compete with carbonate to bind strongly to the uranyl ion to form the complex.

Rao says that there are two unique features in the structure of the uranium–glutarimidedioxime complex. ‘The protons of both oxime groups (–CH=N–OH) are rearranged from the oxygen atom to the nitrogen atom,’ he explains. ‘The middle imide group (–CH–NH–CH–) is deprotonated, resulting in a -1 charged ligand that coordinates to the uranyl cation in a tridentate mode (via the two oxime oxygen atoms and the imide nitrogen atom).’ With such a configuration, he adds, the electron density on the ligand could be delocalised, forming a conjugated system that coordinates strongly to the uranyl cation.

‘It will be interesting to learn how the ligand performs in competition with a peroxide anion, which forms an even stronger complex than carbonate with the uranyl ion in the natural marine photic zone,’ says Mark Antonio, a separation science expert from Argonne National Laboratory, US. He adds that the results from the investigation provide insights that may lead to a viable sequestration of uranium from amongst a myriad other cations.

‘Uranium availability becomes even more important as developing countries such as China and India are ramping up their nuclear power capacities,’ says Wenbin Lin, whose group from the University of North Carolina at Chapel Hill, US, focuses on addressing  fundamental chemical problems relevant to societal issues. ‘If an economically viable technology can be developed to extract uranium from seawater, nuclear power becomes a virtually sustainable clean energy source.’

Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime
Guoxin Tian,  Simon Teat,  Zhiyong Zhang and Linfeng Rao
Dalton Trans., 2012
DOI: 10.1039/C2DT30978E

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Compound 1000 times more effective than first choice drug for parasitic disease

Scientists in Mexico have devised a new synthetic pathway to a nitrogen-containing ligand, which, when bound to divalent nickel or manganese, is a 1000 times more effective than the leading clinical drug at reducing the profileration of the parasite responsible for amoebiasis. This disease causes 70 thousand deaths a year.

Potential cytotoxic and amoebicide activity of first row transition metal compounds

The same ligand bound to other divalent metal ions also shows remarkable anti-cancer properties with activities superior to cisplatin.

Want to know more? Download the article now…
Potential cytotoxic and amoebicide activity of first row transition metal compounds with 2,9-bis-(2′,5′-diazahexanyl)-1,1-phenanthroline (L1)
Juan Carlos García-Ramos, Yanis Toledano-Magaña, Luis Gabriel Talavera-Contreras, Marcos Flores-Álamo, Vanessa Ramírez-Delgado, Emmanuel Morales-León, Luis Ortiz-Frade, Anllely Grizett Gutiérrez, Adriana Vázquez-Aguirre, Carmen Mejía, Julio César Carrero, Juan Pedro Laclette, Rafael Moreno-Esparza and Lena Ruiz-Azuara

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