Posts Tagged ‘Dalton’

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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Top ten most accessed articles in June

This month sees the following articles in Dalton Transactions that are in the top ten most accessed:-

Copper (I) complexes with bipyridyl and phosphine ligands: a systematic study
Inmaculada Andrés-Tomé ,  John Fyson ,  Fernando Baiao Dias ,  Andy P. Monkman ,  Giuliano Iacobellis and Paolo Coppo Dalton Trans., 2012,41, 8669-8674 DOI: 10.1039/C2DT30698K     

Recent progress in the synthesis of inorganic nanoparticles 
C. N. R. Rao ,  H. S. S. Ramakrishna Matte ,  Rakesh Voggu and A. Govindaraj 
Dalton Trans., 2012,41, 5089-5120 DOI: 10.1039/C2DT12266A     

Cycloruthenated Sensitizers: Improving the Dye-Sensitized Solar Cell with Classical Inorganic Chemistry Principles 
Kiyoshi C. D. Robson ,  Paolo G. Bomben and Curtis P. Berlinguette  
Dalton Trans., 2012,41, 7814-7829 DOI: 10.1039/C2DT30825H     

Epitaxial growth and electrochemical properties of Li4Ti5O12 thin-film lithium battery anodes  
Masaaki Hirayama ,  Kyungsu Kim ,  Takeshi Toujigamori ,  Woosuk Cho and Ryoji Kanno  
Dalton Trans., 2011,40, 2882-2887 DOI: 10.1039/C0DT01477J    

Aluminum complexes of the redox-active [ONO] pincer ligand 
Géza Szigethy and Alan F. Heyduk  
Dalton Trans., 2012,41, 8144-8152 DOI: 10.1039/C2DT30295K     

Transition Metal Complexes Meet the Rylenes 
Felix N. Castellano  
Dalton Trans., 2012,41, 8493-8501 DOI: 10.1039/C2DT30765K     

Nothing frustrating about “Frustrated Lewis pairs” 
Douglas W. Stephan  
Dalton Trans., 2012,41, 9015-9015 DOI: 10.1039/C2DT90093A     

Synthesis of Electroactive Multinuclear Dipyrrinato Complexes and Fe(III) Assisted Formation of ?-Alkoxy Substituted 5-Ferrocenyldipyrromethenes 
Rakesh Kumar Gupta ,  Rampal Pandey ,  Sanjeev Sharma and Daya Shankar Pandey  
Dalton Trans., 2012,41, 8556-8566 DOI: 10.1039/C2DT30212H     

Charge-Transfer Guest Interactions in Luminescent MOFs: Implications for Solid-state Temperature and Environmental Sensing 
Patrick L. Feng ,  Kirsty Leong and Mark D. Allendorf  
Dalton Trans., 2012,41, 8869-8877 DOI: 10.1039/C2DT30649B     

Why Nature chose Mn for the Water Oxidase in Photosystem II 
Ron J. Pace ,  Rob Stranger and Simon Petrie  
Dalton Trans., 2012,41, 7179-7189 DOI: 10.1039/C2DT30185G     

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Dalton Transactions? Then why not submit to us today or alternatively email us  your suggestions.

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Frontier and Perspectives in Molecule-Based Quantum Magnets

Photo 1. The participants of the 62nd Fujihara Seminar

The 62nd Fujihara Seminar titled “Frontier and Perspectives in Molecule-Based Quantum Magnets” was held this spring in Sendai, Japan. The Seminar was organized and hosted by Professor Masahiro Yamashita from Tohoku University with the financial support from the Fujihara Foundation of Science. The Fujihara Foundation of Science was founded in 1959 by Mr. Ginjiro Fujihara, the former president of Oji Paper Co. Ltd. who revolutionized the paper industry in Japan and has been recognized as “King of Paper-making”. The main goal of the Fujihara Foundation of Science is to encourage cutting-edge research, leading to significant scientific and technological progress in Japan.
 
The Fujihara Seminars are usually held at Tomakomai in Hokkaido, where the headquarters of Oji Paper Company is located. This year, however, the Council of the Foundation agreed to make an exception and decided to hold the 62nd Fujihara Seminar in Sendai – the heart of Tohoku area, which was struck last year by the destructive earthquake, followed by a devastating tsunami and the Fukushima nuclear power plant disaster – to support its recovery. The Fujihara Foundation of Science covered all expenses of the Seminar including travel fees, accommodation and organization expenses.
 
Thirty leading scientists in the field of molecular quantum magnetism from all over the world accepted the invitation and participated in this fascinating scientific event (Photo 1). The Scientific program featured 29 lectures covering all recent aspects in the development of molecular quantum magnets, introduction of multifunctionality into these systems, and the yet unexplored blank spots on the map of quantum magnetism. The atmosphere of the seminar allowed for many fruitful discussions and for significant strengthening of the molecular magnetism community. The scientific level of the talks was very high, most of the presented results were very recent, sometimes not yet published and stimulated vigorous discussions about the future possible developments and directions in quantum magnetism. The talks given at the 62nd Fujihara Seminar are subject of the special issue of Dalton Transactions titled “Frontiers and Perspectives in Molecule-Based Quantum Magnets”, due to be published later this year.

Photo 2. Discussion between Professor Masahiro Yamashita and Professor Dante Gatteschi

Professor Masahiro Yamashita (Tohoku University, Japan) opened the seminar with a lecture on the history of Single-Molecule (SMM) and Single-Chain (SCM) Magnets. Despite the fact that most of the participants were already familiar with the development of the concept, such introduction based on the “milestones” of quantum magnetism offered a valuable insight into the past, present, and future directions of the field. One future direction was introduced in the second talk given by Professor George Christou (University of Florida, USA). Prof. Christou noted that, for future applications of molecular quantum magnets in spin-based quantum computation and spintronic devices, coupling of two or more SMMs to each other is essential. Such coupling must be very weak in order to maintain the intrinsic quantum properties of each individual SMM, but strong enough to allow them to “feel each other”. Professor Christou presented several examples of SMM aggregates coupled with specially designed organic ligands. Some of them display an exchange-bias of the quantum tunneling of magnetization steps in the hysteresis loops, which is a hallmark of weak interactions between SMM units. 

Photo 3. Informal discussions during the excursion to Hiraizumi – a World Heritage site

In the subsequent talk, Professor Michel Verdaguer (Université Pierre et Marie Curie, France) discussed early results in the field of SCMs and the usefulness of X-Ray Magnetic Circular Dichroism (XMCD) in the characterization of magnetic molecules (especially those deposited on various surfaces). He also presented research on the salicyamidoxime-based Mn6 SMMs and summarized the successes and failures of the cyanide chemistry of transition metals in the field of high-spin molecules and SMMs. 

Professor Dante Gatteschi, one of the founding fathers of molecular magnetism (Univeristà degli Studi di Firenze, Italy) gave the last talk of the first day. Professor Gatteschi summarized the last 30 years of research in the field of nanomagnetism by focusing on the comparison of molecular nanomagnets MNMs with magnetic nanoparticles MNPs. He pointed out that there are still blank spots on the map of MNMs and strongly encouraged the exploration of the no man’s land of magnetic molecules comprising 100–1000 paramagnetic ions. In addition, he reminded the participants that there is “plenty of room” in between the MNMs and MNPs regimes. Synthesis and investigation of 100–1000 ion clusters might be challenging, but the emergence of new fascinating physical phenomena is expected (Photo 2). 

The second day of the Seminar was also filled with extremely stimulating talks and discussions. The lecture of Professor Song Gao (Peking University, China) reflected the strong current trend in molecular quantum magnetism to re-discover the importance of rare-earth elements in the design of SMMs with enhanced characteristics. Professor Gao pointed out that, thanks to the large spin-orbit coupling effect, several mononuclear lanthanide or actinide complexes have been found to be  single ion magnets. Lanthanide-based SMMs seem to be the most promising from an application point of view. Especially the double decker complex TbPc2 (Pc = phthalocyanine) with high single-ion anisotropy and a very high blocking temperature is particularly appealing for the construction of supramolecular spintronic devices, according to Professors Mario Ruben (Université de Strasbourg, France and Karlsruhe Institute of Technology, Germany) and Masahiro Yamashita (Tohoku University, Japan), who gave the last two talks. Professor Ruben demonstrated the potential of TbPc2 in the construction of spin-valves, and Professor Yamashita showed, for the first time, that TbPc2 could act as single-molecule memory device.

The third and last day of the conference was designated as an informal discussion day. The participants could freely interact during an excursion to Hiraizumi (a World Heritage site) – temples, gardens and archeological sites representing the Buddhist Pure Land – and during a river cruise (Photo 3). 

The 62nd Fujihara Seminar ended with a banquet at Shozankan. This final event began with a traditional ceremony of kagami biraki – opening of wooden casks of iwai-zake (“celebration sake”) (Photo 4). During the Banquet the host, Professor Masahiro Yamashita, asked all the participants to visit Sendai again in three years during the next conference on Molecular Quantum Magnets to “report” their advances in this particular field. He suggested that the next meeting would be a great opportunity to verify how fruitful the discussions and new ideas spawned during the 62nd Fujihara Seminar have been. 

 

Photo 4. Ceremony of kagami biraki – opening of wooden casks of iwai-zake (“celebration sake”) – during the Seminar Banquet. 

In summary, the 62nd Fujihara Seminar “Frontier and Perspectives in Molecule-Based Quantum Magnets” was a great opportunity for the top molecular magnetism scientists to interact and discuss how to further advance the field. Look out for the upcoming themd issue later this year.
                                                                                                    

Written by Dr. Dawid Pinkowicz (Tohoku University)

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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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Hydrazine based hydrogen storage materials

This recent Dalton Transactions cover is by Nikolas Kaltsoyannis and team from UCL and my PhD supervisor, David Antonelli. Doing a PhD in hydrogen storage materials myself, I thought that this would be a good opportunity to blog about some of our group’s research…

The big challenge in hydrogen storage materials research is to develop materials that have a high storage capacity, are fully reversible, and can operate at ambient temperature and pressure. Our group have previously reported chromium hydrazide gels that store hydrogen via the Kubas interaction.  The material has a gravimetric hydrogen storage performance of 3.2 wt% at 298K which corresponds to a volumetric capacity of 40.8 kg H2/m3, meeting the US Department of Energy’s 2015 target for volumetric density (40 kg/m3).

In this latest Dalton Transactions article, the Cr(II) binding sites were studied computationally to further study the interaction with H2. Strong evidence suggests that the metal-H2 interaction is Kubas type (confirming our previously reported results) – the Kubas interaction between a transition metal and H2 involves σ-donation from the filled H‑H σ-bonding orbital into an empty transition metal d orbital, and is strengthened by back-donation from a filled metal d orbital into the vacant σ*  orbital of the H2 molecule. The binding model is similar to the Dewar-Chatt-Duncanson model for the bonding of CO ligands to transition metals.

Kaltsoyannis and team extended the system to incorporate other transition metal binding sites: Ti(II), V(II) and Mn(II). They found that H2 did not bind to Mn(II) suggesting that Mn(II) materials may not perform well for hydrogen storage. Hydrogen did bind to V(II) and Ti(II) and calculations indicate 5 and 7 wt% gravimetric storage respectively, surpassing the DOE’s goal for gravimetric storage.

This paper shows that materials based on V(II) and Ti(II) could potentially perform better than the experimentally-realised chromium hydrazide gels.

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

The Kubas interaction in M(II)  (M = Ti, V, Cr) hydrazine-based hydrogen storage materials: a DFT study
Claire V. J. Skipper, Ahmad Hamaed, David M. Antonelli and Nikolas Kaltsoyannis

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Frustrated Lewis pairs themed issue now published

We strongly recommend you have a browse of Dalton Transactions’ latest themed issue in Frustrated Lewis Pairs.

As Guest Editor, Doug Stephan says in his Editorial: there’s nothing frustrating about frustrated Lewis pairs! Particularly as these highly reactive compounds are gaining increasing attention from researchers wishing to activate dihydrogen, olefins, disulfides, CO2… the list continues…

The issue contains 18 articles dedicated to the topic – a small selection is below:

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

Frustrated Lewis pair addition to conjugated diynes: Formation of zwitterionic 1,2,3-butatriene derivatives
Philipp Feldhaus, Birgitta Schirmer, Birgit Wibbeling, Constantin G. Daniliuc, Roland Fröhlich, Stefan Grimme, Gerald Kehr and Gerhard Erker

Fixation of carbon dioxide and related small molecules by a bifunctional frustrated pyrazolylborane Lewis pair
Eileen Theuergarten, Janin Schlösser, Danny Schlüns, Matthias Freytag, Constantin G. Daniliuc, Peter G. Jones and Matthias Tamm

Access the issue here

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Winners at the X Congresso del Gruppo Interdivisionale di Chimica Organometallica

Blerina Gjoka (left) and Daniela Intrieri (right) after winning their Dalton Transactions Poster Prizes at the X Co.G.I.C.O

Blerina Gjoka (left) and Daniela Intrieri (right) after winning their Dalton Transactions Poster Prizes at the X Co.G.I.C.O

The Congresso del Gruppo Interdivisionale di Chimica Organometallica della Societa’ Chimica Italiana (Co.G.I.C.O) recently held their 10th meeting in the beautiful city of Padua, in the North of Italy. Founded in 1991, the group meets every 2 years to discuss recent developments in the field of organometallic chemistry

Attracting established international scientists and young researchers alike, this year the delegates enjoyed a range of talks from the plenary speakers: 

Paul J. Dyson, Lausanne, “Organoruthenium agents for the treatment of invasive tumours” 

Steven P. Nolan, St Andrews, “Recent advances in late transition metal-NHC mediated catalysis” 

Kay Severin, Lausanne, “Chemistry with organometallic half-sandwich complexes: sensors, nanostructures, and catalysts” 

Christophe Coperet, Zurich, “Control functionalization of surfaces towards single-site catalysts” 

Poster sessions were also held during the meeting and we are delighted to announce that the winners of the two Dalton Transactions Poster Prize’s were Daniela Intrieri of Università degli Studi di Milano, and Blerina Gjoka of Università degli studi di Padova. 

Daniela’s poster was on the topic of ‘Ru(TPP)CO-Catalysed 2-Azido Biaryls Annulation to Afford Phenanthridine and Dihydrophenanthridine Derivatives’, and Blerina’s on ‘Iron(III) Amino Triphenolate Complexes as Catalysts for CO2 Fixation’

See the conference homepage for more details

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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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Highlights from themed issues covering metal–organic frameworks

MOF's Metal organic frameworks coordination polymers

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The exciting chemistry of metal-organic frameworks (MOF’s) attracts interest from a range of communities within the chemical sciences. Recently  the Journal of Materials Chemistry published a themed issue ‘Integrating functionality into metal–organic frameworks’ and Dalton Transactions ‘Coordination chemistry in the solid state’.

You can see the full issues by clicking on the links above, alternatively you can browse the highlights below, which are free to download until the 27th July.

Metal–organic frameworks as scaffolds for the encapsulation of active species: state of the art and future perspectives
Jana Juan-Alcañiz, Jorge Gascon and Freek Kapteijn
J. Mater. Chem., 2012,22, 10102-10118
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Supramolecular isomers of metal–organic frameworks: the role of a new mixed donor imidazolate-carboxylate tetradentate ligand
Victoria J. Richards, Stephen P. Argent, Adam Kewley, Alexander J. Blake, William Lewis and Neil R. Champness
Dalton Trans., 2012, 41, 4020-4026

Effect of the organic functionalization of flexible MOFs on the adsorption of CO2
Thomas Devic, Fabrice Salles, Sandrine Bourrelly, Béatrice Moulin, Guillaume Maurin, Patricia Horcajada, Christian Serre, Alexandre Vimont, Jean-Claude Lavalley, Hervé Leclerc, Guillaume Clet, Marco Daturi, Phillip L. Llewellyn, Yaroslav Filinchuk and Gérard Férey
J. Mater. Chem., 2012, 22, 10266-10273

Highly oriented surface-growth and covalent dye labeling of mesoporous metal–organic frameworks
Florian M. Hinterholzinger, Stefan Wuttke, Pascal Roy, Thomas Preuße, Andreas Schaate, Peter Behrens, Adelheid Godt and Thomas Bein
Dalton Trans., 2012, 41, 3899-3901

Structural flexibility and intrinsic dynamics in the M2(2,6-ndc)2(dabco) (M = Ni, Cu, Co, Zn) metal–organic frameworks
Nicole Klein, Herbert C. Hoffmann, Amandine Cadiau, Juergen Getzschmann, Martin R. Lohe, Silvia Paasch, Thomas Heydenreich, Karim Adil, Irena Senkovska, Eike Brunner and Stefan Kaskel
J. Mater. Chem., 2012, 22, 10303-1031

MOF's Metal organic frameworks coordination polymersHydrogen adsorption in the metal–organic frameworks Fe2(dobdc) and Fe2(O2)(dobdc)
Wendy L. Queen, Eric D. Bloch, Craig M. Brown, Matthew R. Hudson, Jarad A. Mason, Leslie J. Murray, Anibal Javier Ramirez-Cuesta, Vanessa K. Peterson and Jeffrey R. Long
Dalton Trans., 2012, 41, 4180-4187

You might also be interested in the recent CrystEngComm Highlight

Coordination polymers, metal–organic frameworks and the need for terminology guidelines
Stuart R. Batten, Neil R. Champness, Xiao-Ming Chen, Javier Garcia-Martinez, Susumu Kitagawa, Lars Öhrström, Michael O’Keeffe, Myunghyun Paik Suh and Jan Reedijk
CrystEngComm, 2012, 14, 3001-3004

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Articles from around the world: Korea

This month we are highlighting some of the excellent articles published in Dalton Transactions from South Korea.

Click on the links below to download the articles…

A double-walled triangular metal-organic macrocycle based on a [Cu2(COO)4] square paddle-wheel secondary building unit
Xiaokai Song, Xinfang Liu, Minhak Oh and Myoung Soo Lah
Dalton. Trans., 2010, 39, 6178–6180

Preparation and characterisation of divalent hard and soft metal (M = Ca, Co, Cu, Zn, Cd, Hg and Pb) complexes of 1,10-dithia-18-crown-6: structural versatility
In-Hyeok Park, Ki-Min Park and Shim Sung Lee
Dalton Trans., 2010, 39, 9696–9704

Self-assembled molecular squares containing metal-based donor: synthesis and application in the sensing of nitro-aromatics
Vaishali Vajpayee, Hyunuk Kim, Anurag Mishra, Partha Sarathi Mukherjee, Peter J. Stang, Min Hyung Lee, Hwan Kyu Kim and Ki-Whan Chi
Dalton Trans., 2011,40, 3112–3115

Two-dimensional metal–organic frameworks with blue luminescence
Seong Huh, Suhyun Jung, Youngmee Kim, Sung-Jin Kim and Seongsoon Park
Dalton Trans., 2010, 39, 1261–1265

Canted antiferromagnetism and spin reorientation transition in layered inorganic–organic perovskite (C6H5CH2CH2NH3)2MnCl4
Seong-Hun Park, In-Hwan Oh, Sungil Park, Younbong Park, Ji Hyun Kim and Young-Duk Huh
Dalton Trans., 2012, 41, 1237–1242

Self-assembled metalla-bowls for selective sensing of multi-carboxylate anions
Anurag Mishra, Vaishali Vajpayee, Hyunuk Kim, Min Hyung Lee, Hyunji Jung, Ming Wang, Peter J. Stang and Ki-Whan Chi
Dalton Trans., 2012, 41, 1195–1201

Anion variation on a cobalt(III) complex of salen-type ligand tethered by four quaternary ammonium salts for CO2/epoxide copolymerization
Jina Yoo, Sung Jae Na, Hyeong Cheol Park, Anish Cyriac and Bun Yeoul Lee
Dalton Trans., 2010, 39, 2622–2630

Why not check out last year’s New Talent: Asia themed issue for more articles from Korea and beyond?

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