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Opening the door to poly(ionic liquid)s with enhanced properties

Poly(ionic liquid)s, or PILs, are polyelectrolytes whose potential uses are being investigated for a variety of technologies, such as batteries, membranes, solar cells and switchable surfaces. In this ChemComm communication, Professor Eric Drockenmuller and co-workers at the Université de Lyon, University of Liège and the Institut Universitaire de France describe a new family of PILs based on poly(vinyl ester 1,2,3-triazolium)s, which should give rise to new properties and application possibilities. 

The materials are prepared from a multistep route making use of `click chemistry´(copper(I) catalysed azide alkyne Huisgen cycloaddition reaction), palladium catalyzed vinyl group exchange, and cobalt mediated radical polymerisation. This route yields a neutral polymer, which is transformed into the poly(ionic liquid) using N-methyl bis[(trifluoromethyl)sulfonyl]imide. This useful reagent alkylates the triazole group present, and delivers the bis[(trifluoromethyl)sulfonyl]imide counterion in one step. 

Synthetic route used to yield new poly(vinyl-ester 1,2,3-triazolium)s

The ionic conductivity for the PIL reported is slightly lower than for other types of PIL. To tune this property, a variety of alkynes and azides are being tested in the ring forming step of the reaction, which will result in different substituents on the triazolium ring and on the spacer group between the polymer backbone and triazolium ring.  Changes in thermal properties in the the neutral precursor-to-PIL stage of the reaction were measured using broadband dielectric spectroscopy. Significant changes in solubility, and a 9⁰C rise in glass transition temperature to -16⁰C, were observed. 

The molecular variety introduced by this new synthetic approach offers large scope for fine tuning the electronic and mechanical material properties of these polyelectrolytes, further enabling their use in important technological applications. 

Read this Chemical Communication today – it’s free to access until 3rd April*: 

Poly(vinyl ester 1,2,3-triazolium)s: a new member of the poly(ionic liquid)s family
M. M. Obadia, G. Colliat-Dangus, A. Debuigne, A. Serghei, C. Detrembleurb and E. Drockenmuller
DOI: 10.1039/c4cc08847f 

*Access is free through a registered RSC account – click here to register

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Improvements to a selective hydrogenation process using ionic liquids

In this ChemComm communication, Peter Claus and co-workers describe an interesting application of room temperature ionic liquids to the selective hydrogenation of 2-hexyne. Unlike many reports in the literature, where an ionic liquid acting as a solvent may enhance a particular reaction, this report outlines a solid supported catalyst system modified with an ionic liquid layer.

Such materials, known as SCILLS, (solid catalyst with an ionic liquid layer) have been investigated in a variety of hydrogenation reactions. In this work the desired reaction is the reduction of 2-hexyne to cis-2-hexene. The catalyst is 1 wt% palladium on silica, modified with various loadings of 3 common ionic liquids: BMIM hexafluorophosphate, BMIM bis(triflouoromethanesulfonyl)imide and N-butyl-N-methylpyrrolidinium dicyanamide ([BMPL][DCA]). The performance of the unmodified catalyst was compared with the yield and selectivity afforded by the SCILL systems. The best results were reported with the dicyanamide ionic liquid SCILL, ([BMPL][DCA]) at 30 wt% ionic liquid loading.

In such a process, there are several reactions that must be suppressed. As the product is an olefin, isomerisation to the trans product must be controlled, as must further hydrogenation to the fully reduced material, hexane. For a number of reasons, based on the nature and amount of chemisorbed hydrogen, and favourable dicyanamide anion interactions with palladium, the dicyanamide SCILL system is particularly effective.

Notably, this system gives improved performance in terms of selectivity and yield over the two best performing commercial catalysts for this task. For example, Lindlar´s catalyst, palladium on calcium carbonate, deactivated with lead, cannot match its performance. In this work, the authors give an example of how ionic liquids can add value to a commercial process, while also offering considerable process improvements, in terms of toxicity and arguably, simplicity. The group’s focus now turns to SCILL activity and stability in a continuous hydrogenation process.

Read this RSC Chemical Communication today!

ionic-liquid layer
Frederick Schwab, Natascha Weidler, Martin Lucas and Peter Claus
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Nitrogen-rich Formazanate Ligands: Redox and Coordination Chemistry

In this communication, Edwin Otten and Mu-Chieh Chang from the Stratingh Institute for Chemistry at the University of Groningen describe their work with formazanate ligands. They detail here an easier route to boron difluoride chelates with this type of ligand via an exchange transmetallation from a zinc complex with the same ligand in the presence of boron difluoride etherate (BF3.Et2O).

Formazan, or formazanate in its deprotonated form, is an example of a ‘non-innocent ligand’. Just like transition metals, it has an accessible redox chemistry all of its own, and can effectively store electrons by existing in several oxidation states stabilised by its structure. Chemically, formazanates, with a NNCNN backbone are nitrogen rich analogs of diketiminates, which can be represented by NCCCN. In this case, aryl substitution on the terminal nitrogen and central carbon atoms aid the electron stabilisation.

Crystal structure and cyclic voltammagram of formazanate boron difluoride complex

The mono formazanate boron difluoride complex was readily accessible by mixing a bis formazanate zinc complex with BF3 etherate in hot toluene. Zinc fluoride precipitated from solution and the air stable, crystalline material boron chelate was isolated in high yield. X-ray crystal structure determination was possible, showing a tetrahedral environment around the boron atom, and equal bond lengths in the NNCNN core of the ligand, proving its delocalised nature. An important intermediate of the process was also isolated and identified by this technique aiding mechanism elucidation.

Using cobaltocene as reducing agent, a reduced from of the complex was also isolated and characterised, and use of cyclic voltammetry quantified the redox potentials for formation of the further reduced forms of the material. All three redox states were observed. Applications of these materials in catalysis and further investigation in coordination chemistry are ongoing. The potential for application of such ligands in the area of sensors and devices, or even therapeutics poses many possibilities.

Read this RSC Chemical Communication today – access is free* for a limited time only!

Synthesis and ligand-based reduction chemistry of boron-difluoride complexes with redox-active formazanate ligands
M.-C. Chang and E. Otten
DOI: 10.1039/c4cc03244f

*Access is free until 29th August 2014 through a registered RSC account – click here to register

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Betaine Bistriflimide: F-block chemistry enabled by a stabilizing Ionic Liquid

Due to their low volatility, favourable solvent properties and tunable phase behaviour, ionic liquid (IL) technology continues to attract interest in a wide variety of applications. Over the last few decades, the term ‘task specific ionic liquid’ (TSIL) has appeared, the meaning of which is that the application has been considered more carefully in the design and structure of one or both of the constituent IL ions.

In this ChemComm communciation, researchers from the Los Alamos National Laboratory, New Mexico, USA, describe advances in the application of ILs in the area of nuclear fuel reprocessing. The authors describe how neptunium may exist in solution in +III, +IV, +V and + VI oxidation states. The pentavalent state is the most stable and common, but interestingly, usually the most reluctant to coordinate with ligands, or take part in ion exchange processes.

Ionic liquid molecular structure and stabilizing behaviour towards Np(V) in aqueous solution


In aqeuous solution, in the presence of the ionic liquid betaine bistriflimide, the lifetime of the Np(IV) solution species is significantly increased. This is followed by the presence of a characteristic electronic adsorption at 970nm. Without the IL, an anti-oxidant is required to keep the metal from converting to its +V form. Np(V) has a rich and complex coordination chemistry at room temperature, so the authors repeated experiments with sources of  Np(V) at 60oC. After 3 days, 90% of the starting neptunium compound had been converted to the betaine complexed form, compared with a 15% conversion at room temperature. Again the material was stable in solution, not resulting in Np(IV) species unless a reducing agent such as hydrazine was deliberately added.

With this detailed study, the authors significantly add to the body of knowledge of competitive coordination chemistry of actinides in aqueous solutions of ionic liquids. This should, in turn, enable new separation technology R&D for the important task of nuclear fuel reprocessing.

Read this ChemComm communication for free* today!

Unusual redox stability of neptunium in the ionic liquid [Hbet][Tf2N]
Kristy Long, George Goff and Wolfgang Runde
DOI: 10.1039/C4CC01835D

*Access is free untill Friday 6th June through a registered RSC account – click here to register


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Appetite for Conformity: Precise Graphene Nanoribbons

Graphene nanoribbons (GNRs) are ultra-thin strips of graphene which exhibit technologically relevant optical, electronic and magnetic properties. How well these properties can be defined, understood and exploited depends on how precisely these ‘GNRs’ can be prepared. Top-down approaches to realise these materials from, for example, graphite, graphene or carbon nanotubes have been developed over recent years. However, the resultant  materials are typically non-uniform, being wide, (relatively speaking) with a large amount of disorder.

In this ChemComm communication, Alexander Sinitskii and co-workers from the University of Nebraska and collaborators from the University of Puerto Rico report an elegant, controlled, bottom-up solution synthesis of well defined nitrogen doped graphene nano-ribbons. Though the materials produced are extremely insoluble, they have been extensively characterised via a range of surface analytical techniques.

The synthesis itself centres around the 3 step preparation of a multi-aryl containing dibromo pyrimidine monomer which is polymerised via a Yamamoto coupling using a nickel catalyst. The desired graphene  structure is delivered via a cyclodehydrogenation Scholl reaction using ferric chloride. The molecular control from this route yields a very well defined structure. The only disorder introduced is a symmetrical one due to alternate possible sites for the  four constituent nitrogen atoms present in each unit cell.

Synthetic route to well defined nitrogen doped graphene nanoribbons (4N-GNRs)

The 4N-GNR materials were deposited on a variety of supports to enable microscopic and surface analytics such as AFM, STM, TEM, XPS, EDX and Raman spectroscopy. The materials were observed to take on a ‘nanobelt’ conformation on deposition from sonicated dispersions. Particularly striking is the improvement in the fine structure reported in the Raman spectra, compared with typical signals for less well defined carbon materials, confirming the structural quality of the 4N-GNRs produced.

This communication will doubtless prove important to the development of sustainable synthetic routes to well defined graphene nanoribbons, enabling  further study of the fascinating properties of these exciting new materials.

Read this RSC Chemical Communication today – access is free* for a limited time only!

Bottom-up solution synthesis of narrow nitrgoen-doped graphene nanoribbons
Chem. Commun., 2014,50, 4172-4174
DOI: 10.1039/C4CC00885E

*Access is free untill the 19th May through a registered RSC account – click here to register

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A new, functionally tolerant route to organo-aluminium reagents

Paul Knochel and colleagues at the Ludwig Maximilians University in Munich have reported a new general synthesis of aryl and heteroaryl aluminium reagents.  The route described allows a larger range of functional groups to be incorporated, compared with the more usual approach of inserting Al into aryl halide bonds directly.  The synthetic methodology uses di-isobutyl aluminium chloride and n-BuLi at -78C in an exchange reaction with a functionalised aryl or heteroaryl halide.

General scheme for preparation and derivitisation of aryl aluminium reagents

The synthesis of a group of derivatives is described, via the reaction of the aluminium reagents with a variety of electrophiles.  Typical cross coupling reactions using palladium catalysis, as well as copper-catalysed Michael additions, allylation and acylations are reported, involving a rich variety of incorporated functional groups. Importantly, further derivitisation of the organo-aluminium reagents includes no further transmetalation steps.

Of note are the reactivities of electron-rich furan and thiophene bromides functionalised with ester groups, which also could remain intact during the reaction with di-isobutylaluminium chloride and butyl-lithium at -78C, yielding the desired reagents that were further derivatised, as in other examples.

N-heterocycles such as 3-bromo-quinoline also received attention, yielding the aluminium reagent in 73% yield, and smoothly converting in a palladium catalysed cross coupling reaction with 4-iodobenzonitrile.  Full NMR data for the products of the reactions described is given in the supplementary information.

In general, this Communication describes a considerable step forward in the field of organo-aluminium reagents for organic synthesis, and no doubt will be of interest to synthetic chemists in many fields.

Read this HOT ChemComm article today!

Generation of Functionalised Aryl and Heteroaryl Aluminium Reagents by Halogen/Lithium Exchange
Thomas Klatt, Klaus Groll and Paul Knochel
Chem. Commun., 2013,49, 6953-6955
DOI: 10.1039/C3CC43356K, Communication

Kevin Murnaghan is a guest web-writer for Chemical Communications. He is currently a Research Chemist in the Adhesive Technologies Business Sector of Henkel AG & Co. KGaA, based in Düsseldorf, Germany. His research interests focus primarily on enabling chemistries and technologies for next generation adhesives and surface treatments. Any views expressed here are his personal ones and not those of Henkel AG & Co. KGaA.

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