Archive for the ‘Hot Articles’ Category

Delivering cancer-combatting compounds

caged pyrenyl arene ruthenium complexScientists 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

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

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

Computational studies of complexation of nitrous oxide by borane–phosphine frustrated Lewis pairsThomas 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

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.

mixed metal porphyrin

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

Model of the YPK9 proteinIn 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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Exchanging ligands on semiconducting nanocrystals

Semiconductors are at the heart of nearly all things computerised, and with nearly all things computerised that makes semiconductors important. Semiconducting nanocrystals have become an interesting area of research because as colloidal inks they can potentially be used to easily print onto substrates to create photo-voltaic devices or a broad range of electronic devices.

CdSe nanocrystals undergoing ligand exchange and thermolysis

CdSe nanocrystals undergoing ligand exchange and thermolysis

This Hot Communication from the Brutchey group details the use of a ligand which exchanges with the capping ligand of semiconducting CdSe nanocrystals making them highly dispersible in a range of polar solvents (in DMF a stable colloid forms for > 2 weeks). Under mild conditions thermolysis transforms the surface bound ligands to thiocyanate in situ, producing nanocrystal films of CdSe(SCN). There are also indications of improved inter-particle coupling…

Nanocrystal ligand exchange with 1,2,3,4-thiatriazole-5-thiolate and its facile in situ conversion to thiocyanate
David H. Webber and Richard L. Brutchey

This Hot Article is part of our up-coming themed issue ‘New Talent Americas’, Guest Edited by Dan Mindiola and John Arnold, other articles due to be published in this special issue include:

Perceiving Molecular Themes in the Structures and Bonding of Intermetallic Phases: The Role of Hückel Theory in an Ab Initio Era
Timothy E. Stacey and Daniel Fredrickson

Splitting water with rust: hematite photoelectrochemistry
Thomas W. Hamann

A heterobimetallic metal–organic framework with tunable 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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Nanocatalyst for hydrogen release

hydrogen release from the dimethlyamine-borane complexAmine borane complexes are a promising solution for storing hydrogen, particularly as we move towards a hydrogen economy. Whilst focusing on developing the dehydrogenation of such complexes (namely dimethylamine-borane), scientists from Turkey have shown that you need to think small to think big by preparing a nanoparticle catalyst for the reaction.

By adding ruthenium (III) chloride to the hydrogen storing dimethlyamine-borane complex, the team found that ruthenium nanoparticles are generated in-situ which further work to catalyse the release of hydrogen from the complex.

Nanosizing the catalyst means a higher proportion of surface atoms are available for the hydrogen-storage complex – the result is greater catalytic activity and faster hydrogen generation.

Read the HOT article now for free… Hydrogen liberation from the hydrolytic dehydrogenation of dimethylamine–borane at room temperature by using a novel ruthenium nanocatalyst
Salim Caliskan, Mehmet Zahmakiran, Feyyaz Durap and Saim Özkar

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Ion Uptake and Solid Solution Formation

The study of ion-mineral interactions is a fascinating topic which spans many disciplines from inorganic chemistry to geology and ancient history. The driving forces behind the interaction of an ion and a mineral are complex, and whether or not an ion becomes incorporated into the solid phase is determined by many factors.

celestite strontianite Eu3+ Cm3+ Eu Cm solid solution solid-solution

 This Hot paper by Kiel Holliday et al. looks at the coordination of Eu and Cm to investigate what role local symmetry, ligand strength and a range of other parameters have in solid solution formation in both Eu- and Cm-doped strontianite and celestite.

So what is solid solution formation dependent on and what factors influence it?

Discriminating factors affecting incorporation: comparison of the fate of Eu3+–Cm3+ in the Sr carbonate–sulfate system
Kiel Holliday, Aurélie Chagneau, Moritz Schmidt, Francis Claret, Thorsten Schäfer and Thorsten Stumpf
Journal Article
Dalton Trans., 2012, 41, 3642-3647
DOI: 10.1039/C2DT12425D

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Vapour sorption with no loss of crystallinity

A recent article from John Field and his team at the University of KwaZulu-Natal, South Africa, describes the sorption and sensing properties of a porous material with an unusual crystal structure. The platinum based material has an open framework made up from repeating 2D stacks of [Pt{4′-(Ph)trpy}(NCS)]+ cations (where trpy is 2,2′:6′,2″-terpyridine) that are stabilised by extended π-π interactions. This is somewhat different to the usual coordination compounds that are formed from metal ions linked by bridging organic molecules.

Unlike it’s parent material ([Pt(trpy)(NCS)]SbF6), this compound can reversibly sorb and desorb organic vapours with no disruption of the framework structure which the team attribute to the 4′-phenyl substituent which participates in stabilising π-π interactions with pyridines on the nearby cations.

solvent accessible voids in [Pt{4'-(Ph)trpy}(NCS)]SbF6

The solvent accessible voids in [Pt{4′-(Ph)trpy}(NCS)]SbF6

Read this HOT article now:
Sorption of small molecule vapours by single crystals of [Pt{4′-(Ph)trpy}(NCS)]SbF6 where trpy = 2,2′:6′,2′′-terpyridine: a porous material with a structure stabilised by extended π–π interactions
John S. Field, Orde Q. Munro and Bradley P. Waldron

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Linking up with Mercury

Species featuring group 12 to group 12 bonds have lately become the subject of much interest and discussion, as have species containing homo-nuclear metal to metal bonds. This Hot Communication from Paul Weiss, Shiv Khanna, Ayusman Sen and colleagues details the discovery of a dimeric zintl anion featuring an Hg-Hg bond.

Molecular orbital diagram of the dimeric zintl ion

Molecular orbital diagram of the dimeric zintl ion

The new zintl phase contains [As7HgHgAs7]4− ions with an unsupported Hg-Hg bond, as characterized by cyclic voltammetry, molecular orbital diagram, band gap energy and Raman spectra. To find out more about the group’s findings you can download there paper below, which is free to access for 4 weeks.

On the stability of an unsupported mercury–mercury bond linking group 15 Zintl clusters
Sukhendu Mandal, Arthur C. Reber, Meichun Qian, Ran Liu, Hector M. Saavedra, Saikat Sen, Paul S. Weiss, Shiv N. Khanna and Ayusman Sen
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30083D

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