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March’s HOT articles

24 Mar 2015

Take a look at HOT articles for March. These are only free to acess for 4 weeks only and are available for viewing in a collection on our website.

An ionic liquid process for mercury removal from natural gas
Mahpuzah Abai, Martin P. Atkins, Amiruddin Hassan, John D. Holbrey, Yongcheun Kuah, Peter Nockemann, Alexander A. Oliferenko, Natalia V. Plechkova, Syamzari Rafeen, Adam A. Rahman, Rafin Ramli, Shahidah M. Shariff, Kenneth R. Seddon, Geetha Srinivasan and Yiran Zou
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03273J

Graphical Abstract

Free to access until 24^thApril 2015

Relationship between crystal structure and thermo-mechanical properties of kaolinite clay: beyond standard density functional theory
Philippe F. Weck, Eunja Kim and Carlos F. Jové-Colón
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00590F

Graphical Abstract

Free to access until 23^rdApril 2015

The titanium tris-anilide cation [Ti(N[^tBu]Ar)₃]⁺stabilized as its perfluoro-tetra-phenylborate salt: structural characterization and synthesis in connection with redox activity of 4,4′-bipyridine dititanium complexes
Heather A. Spinney, Christopher R. Clough and Christopher C. Cummins
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00105F

Graphical Abstract

Free to access until 14^thApril 2015

Iridium–bipyridine periodic mesoporous organosilica catalyzed direct C–H borylation using a pinacolborane
Yoshifumi Maegawa and Shinji Inagaki
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00239G

Free to access until 14^thApril 2015

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A Cagey Conundrum

23 Mar 2015

“My original intention in the late 1940s was to spend a few years understanding the boranes, and then to discover a systematic valence description of the vast numbers of electron deficient intermetallic compounds. I have made little progress toward this latter objective,” said the late Professor William N. Lipscomb in his 1976 Nobel acceptance speech.¹

In their recent Dalton Transactions Hot Article, Jose M. Goicoechea and John E. McGrady examine the chemistry of main group cluster-encapsulated transition metal atoms, laying another piece of the foundation of Lipscomb’s “latter objective.”

The authors assign themselves an ambitious task: to provide a system to predict the geometries of cages of the tetrel elements (C, Si, Ge, Sn, Pb) which encapsulate transition metal atoms. They focus on six high-symmetry cage structures, shown below, which have been observed for tetrel-encapsulated metal atoms (denoted M@E_x, for example Ni@Ge₁₂.).

The six three-dimensional cage geometries examined.

Lipscomb’s elegantly-described closo, nido, and arachno borane structures (“closed,”“nest”, and “spider’s web,” respectively) provided an initial basis for classifications of cages. Later, the Wade/Mingos rules laid the foundation for predicting the geometries based on the electronic structure of the cluster.

Goicoechea and McGrady use the total valence electron count – of the tetrel cages, plus the d-electron count of the encapsulated metal – to describe patterns in the structures. Nevertheless, some results defy electron-count classification, for example, the preference of silicon cages to form D_6h-symmetric hexagonal prisms in M@Si₁₂ complexes, in contrast to the M@Ge₁₂ analogues.

It is a broad, big-picture paper, a synthesis of a wide range of experimental and theoretical results. Some structures are known experimentally from x-ray crystallography, some have only been predicted computationally. The authors discuss the varying relevance of considering the d-electron counts of the metals, and technological implications such as quenching of the magnetic moment of encapsulated metal atoms. For me, the scope alone made this a worthwhile read.

Read the full article now:

On the structural landscape in endohedral silicon and germanium clusters, M@Si₁₂ and M@Ge₁₂
José M. Goicoechea and John E. McGrady
Dalton Trans., 2015, DOI: 10.1039/C4DT03573A

¹Lipscomb, W.N. “The Boranes and Their Relatives” in Les Prix Nobel en 1976. Imprimerie Royal PA Norstedt & Soner, Stockholm, 1977

Ian Mallov is currently a Ph.D. student in Professor Doug Stephan’s group at the University of Toronto. His research is focused on synthesizing new Lewis-acidic compounds active in Frustrated Lewis Pair chemistry. He grew up in Truro, Nova Scotia and graduated from Dalhousie University and the University of Ottawa, and worked in chemical analysis in industry for three years before returning to grad school.

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Mercury-grabbing ionic liquids hit the gas

13 Mar 2015

Scientists in the UK and Malaysia have disclosed the research behind a fast and safe commercial technology for removing mercury from natural gas. The technology is the first solid-supported ionic liquid to be used at an industrial scale, and its development, from laboratory to full plant operation, took just four years.

The mercury-removing ionic liquid system was commercialised for use within the petroleum gas production industry

The vast volume of natural gas that is processed annually by industry contains a pernicious contaminant – hundreds of tons of mercury. This corrosive metal is intrinsically present within hydrocarbon deposits, and it must be removed to mitigate catastrophic damage, not only to the environment but also to the gas-processing plants.

Interested? Read the full story at Chemistry World.

The link to the original article is below:

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A collection of papers in memory of Lord Jack Lewis

17 Feb 2015

We are very pleased to announce the launch of a commemorative article collection in memory of Lord Jack Lewis.

Lord Jack Lewis, who recently died aged 86, was the 1970 Inorganic Professor at Cambridge for 25 years from 1970 to 1995. Highly energetic and extremely talented, he was among a small band of pioneers who revolutionised inorganic chemistry and must be regarded as one of the true founding fathers of the modern field. As a tribute to Jack, Brian F. G. Johnson, William. P. Griffith, Robin J. H. Clark, John Evans, Brian H. Robinson and Paul R. Raithby have chosen a selection of his papers that they feel demonstrate Jack’s interest and contribution to inorganic chemistry over the course of his career, introducing them in a special Editorial in Dalton Transactions.

We very much hope that you will enjoy this commemorative article collection.

To access all of the Lewis articles and the Editorial, go to: http://rsc.li/lewis.

Lord Jack Lewis

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February’s HOT articles

13 Feb 2015

This month brings some more HOT articles. These are only free to acess for 4 weeks only and are available for viewing on our website.

Thermoelectric properties of the Zintl phases Yb₅M₂Sb₆ (M = Al, Ga, In)
Umut Aydemir, Alex Zevalkink, Alim Ormeci, Heng Wang, Saneyuki Ohno, Sabah Bux and G. Jeffrey Snyder
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03773A

Graphical Abstract

Free to access until 25^thMarch 2015

Exploring excited states of Pt(II) diimine catecholates for photoinduced charge separation
Paul A. Scattergood, Patricia Jesus, Harry Adams, Milan Delor, Igor V. Sazanovich, Hugh D. Burrows, Carlos Serpa and Julia A. Weinstein
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03466J

Graphical Abstract

Free to access until 25^thMarch 2015

On the structural landscape in endohedral silicon and germanium clusters, M@Si₁₂and M@Ge₁₂
José M. Goicoechea and John E. McGrady
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03573A

Graphical Abstract

Free to access until 9^thMarch 2015

The synthesis, structure, topology and catalytic application of a novel cubane-based copper(II) metal–organic framework derived from a flexible amido tripodal acid
Anirban Karmakar, Clive L. Oliver, Somnath Roy and Lars Öhrström
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03087G

Graphical Abstract

Free to access until 9^thMarch 2015

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Bridging the gap – small ligands in MOFs

06 Feb 2015

In a recent article from the group of Deanna D’Alessandro at the the University of Sydney, Australia, Liang et al. have shown for the first time a 3D metal-organic framework (MOF) comprised solely of the monocarboxylate ligand derived from formic acid, with exceptionally selective CO₂ adsorption properties.

For those involved in MOF chemistry, it is well accepted that in most cases, organic bridging ligands should have at least two coordinating functional groups that link adjacent inorganic secondary building units into a porous crystalline lattice. Therefore, it comes as a complete surprise to find that a porous MOF can be formed entirely of monocarboxylate ligands that are traditionally used to cap and thus prevent further growth of the framework. Through structural characterisation, Liang et al. have shown that the formate takes on two different binding modes within the framework; one that caps the oxyzirconium cluster secondary building units, and another that bridges and interconnects these into a crystalline architecture.

Why is this important, I hear you ask? As the formate ligands are very small, this results in the formation of very small pores that can lead to selectivity in the adsorption of different gases. This is just what has been shown by Liang et al., with adsorption isotherms demonstrating that adsorption of CO₂ is a factor of 145 higher than for N₂. Potential applications may lead to the sequestration and use of greenhouses gases such as CO₂ from the atmosphere.

CO2 and N2 isotherms for ZrFA

Check out the full article now!

The first example of a zirconium-oxide based metal–organic framework constructed from monocarboxylate ligands
Weibin Liang, Ravichandar Babarao, Michael J. Murphya and Deanna M. D’Alessandro
Dalton Trans., 2015, 44, 1516-1519

Christopher Hinde obtained his Masters degree in Chemistry from the University of Southampton, UK in 2011. He is currently doing research towards a Ph.D. in the area of materials chemistry and catalysis under the supervision of both Dr Robert Raja at the University of Southampton and Professor T. S. Andy Hor at the Institute of Materials Research and Engineering (IMRE), part of Singapore’s Agency for Science Technology and Research (A*STAR).

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January’s HOT articles

03 Feb 2015

A new year has brought a new crop of HOT articles for the month. As always, these are free to access for 4 weeks!

Our HOT articles have also been compiled into a collection and are available for viewing on our website.

Methylated Re(I) tetrazolato complexes: photophysical properties and Light Emitting Devices
Melissa V. Werrett, Gregory S. Huff, Sara Muzzioli, Valentina Fiorini, Stefano Zacchini, Brian W. Skelton, Antonio Maggiore, Joanna M. Malicka, Massimo Cocchi, Keith C. Gordon, Stefano Stagni and Massimiliano Massi
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03228D

Graphical Abstract

Free to access until 26^thFebruary 2015

Recent advances towards the fabrication and biomedical applications of responsive polymeric assemblies and nanoparticle hybrid superstructures
Xianglong Hu and Shiyong Liu
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03609C

Graphical Abstract

Free to access until 26^thFebruary 2015

Synthesis and characterization of substituted Schiff-base ligands and their d¹⁰metal complexes: structure-induced luminescence tuning behaviors and applications in co-sensitized solar cells
Yu-Wei Dong, Rui-Qing Fan, Ping Wang, Li-Guo Wei, Xin-Ming Wang, Hui-Jie Zhang, Song Gao, Yu-Lin Yang and Yu-Lei Wang
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03602F

Graphical Abstract

Free to access until 26^thFebruary 2015

Spin-crossover behaviors in solvated cobalt(II) compounds
Shinya Hayami, Manabu Nakaya, Hitomi Ohmagari, Amolegbe Saliu Alao, Masaaki Nakamura, Ryo Ohtani, Ryotaro Yamaguchi, Takayoshi Kuroda-Sowa and Jack K. Clegg
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03743J

Graphical Abstract

Free to access until 26^thFebruary 2015

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Hierarchical functionality in MOF structures

17 Dec 2014

Yanfeng Yue and co-workers have developed a novel method for introducing mesoporosity into a series of metal–organic framework (MOF) materials by using “perturbation-assisted nanofusion”, as described in their recent Dalton Transactions paper. The authors exemplified the importance of their work by showing that large dye molecules can be encapsulated in the mesopores for luminescent sensing of volatile organic compounds (see also the image below, from Yue and co-workers).

Encapsulation of large dye molecules in hierarchically superstructured metal-organic frameworks, for ratiometric sensing

Introducing mesoporosity into microporous frameworks has been of interest to materials chemists for several years, in an effort to expand the functionality and widen the potential applications of nanoporous materials.

Microporous materials have proved to be great tools for achieving precision in catalysis, separations and sensing (among others), by using internal surfaces or porosity in a multitude of ways. However, by introducing mesoporosity, one can overcome certain limitations, such as diffusion or small molecule selectivity, and one can even introduce multifunctionality by using the properties of both the micropores and the mesopores within a structure.

Typical procedures for the fabrication of mesopores in MOF structures involve the use of wasteful techniques such as etching or organic templates. However, rather than building mesopores into single crystals of MOFs, Yue and co-workers take a different approach by constructing mesopores from fused MOF nanocrystals that are formed through a highly agitated synthesis procedure (that is, perturbation-assisted nanofusion). The result is the formation of a robust hierarchical superstructure through an inexpensive and economical process.

This out-of-the-box thinking allows the authors to exploit their new ‘bottom-up’ approach to introduce functional mesoporosity into MOF materials, for the sensing of volatile organic compounds.

It is easy to see how this method would be useful to researchers not only in sensing but also in any of the myriad established and emerging MOF applications.

Read the full article now at:

Encapsulation of large dye molecules in hierarchically superstructured metal–organic frameworks
Yanfeng Yue, Andrew J. Binder, Ruijing Song, Yuanjing Cui, Jihua Chen, Dale K. Hensley and Sheng Dai
Dalton Trans., 2014, 43, 17893-17898

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December’s HOT articles

09 Dec 2014

Enjoy a read of our end of year HOT articles which are free to access for 4 weeks only!

Our HOT articles have also been compiled into a collection and are available for viewing on our website.

A theoretical study of the aromaticity in neutral and anionic borole compounds
J. Oscar C. Jimenez-Halla, Eduard Matito, Miquel Solà, Holger Braunschweig, Christian Hörl, Ivo Krummenacher and Johannes Wahler
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03445G

Free to access until 6^thFebruary 2015

High performing smart electrochromic device based on honeycomb nanostructured h-WO3 thin films: hydrothermal assisted synthesis
Vijay V. Kondalkar, Sawanta S. Mali, Rohini R. Kharade, Kishorkumar V. Khot, Pallavi B. Patil, Rahul M. Mane, Sipra Choudhury, Pramod S. Patil, Chang K. Hong, Jin H. Kim and Popatrao N. Bhosale
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT02953D

Free to access until 6^thFebruary 2015

Application of three-coordinate copper(I) complexes with halide ligands in organic light-emitting diodes that exhibit delayed fluorescence
Masahisa Osawa, Mikio Hoshino, Masashi Hashimoto, Isao Kawata, Satoshi Igawa and Masataka Yashima
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT02853H

Graphical Abstract

Free to access until 6^thJanuary 2015

Na_0.3WO₃nanorods: a multifunctional agent for in vivo dual-model imaging and photothermal therapy of cancer cells
Yuxin Zhang, Bo Li, Yunjiu Cao, Jinbao Qin, Zhiyou Peng, Zhiyin Xiao, Xiaojuan Huang, Rujia Zou and Junqing Hu
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT02927E

Free to access until 6^thJanuary 2015

Transmetalation from B to Rh in the course of the catalytic asymmetric 1,4-addition reaction of phenylboronic acid to enones: a computational comparison of diphosphane and diene ligands
You-Gui Li, Gang He, Hua-Li Qin and Eric Assen B. Kantchev
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03147D

Graphical Abstract

Free to access until 1^stJanuary 2015

A contribution to the rational design of Ru(CO)₃Cl₂L complexes for in vivo delivery of CO
João D. Seixas, Marino F. A. Santos, Abhik Mukhopadhyay, Ana C. Coelho, Patrícia M. Reis, Luís F. Veiros, Ana R. Marques, Nuno Penacho, Ana M. L. Gonçalves, Maria J. Romão, Gonçalo J. L. Bernardes, Teresa Santos-Silva and Carlos C. Romão
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT02966F

Graphical Abstract

Free to access until 1^stJanuary 2015

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Molecular Memory in a Long-Lasting Mixed Spin State Fe(III) Complex

05 Dec 2014

From early on, we are taught to look at linear mathematical relationships as dependent variables that are determined by the value of an independent variable.

The reason that I find the phenomenon of hysteresis fascinating is that it is the violation of the above concept. By definition, the value of a dependent variable showing hysteresis depends not only on the value of the independent variable but also on whether the independent variable has been increasing or decreasing before it arrives at the value at which a measurement is taken. The dependent variable has a ‘memory’ of its path.

Examples of hysteresis are rare on a molecular level. One of several fascinating aspects of the recent Dalton Transactions paper by Guy Jameson and colleagues is that the (temperature-dependent) magnetism exhibited by the authors’ Fe(III) spin-crossover (SCO) complex shows two hysteresis loops; an example from Jameson and colleagues is shown below.

Magnetic Susceptibility vs Temperature Showing Hysteresis

In transition metal complexes where both high spin and low spin states are possible, SCO occurs when a complex switches from one spin state to the other. Unsurprisingly, this is temperature-dependent, hence the temperature dependence of the magnetism. Hysteresis in magnetic measurements of SCO compounds is known, but Jameson and colleagues report a number of rare properties for the Fe(III) compound that they investigate, [Fe(qsal-Br)₂]NO₃•2MeOH (where qsal-Br denotes the (N-8-quinolyl)-5-bromo-salicylaldimate ligand).

The vast majority of complexes in which SCO occurs exhibit the phenomenon in a single step — at a certain temperature, all of the molecules in a bulk sample will convert from one spin state to the other. This is only the fifth example of a mononuclear Fe(III) complex that shows full SCO that occurs in two or more discrete increments where symmetry is lost within the molecular structure. In the case of this Fe(III) complex, the temperature range over which some metal nuclei are high spin, and some are low spin (in this case 50% each), is the largest ever reported for a mixed spin-state Fe(III): that is, 96 K.

Here, both steps exhibit hysteresis. The spin-state transitions occur at different temperatures when the authors start with the complex at 300 K and cool it, versus when they warm the complex from 4 K.

Read the full article at:

Abrupt two-step and symmetry breaking spin crossover in an iron(III) complex: an exceptionally wide [LS–HS] plateau
David J. Harding, Wasinee Phonsri, Phimphaka Harding, Keith S. Murray, Boujemaa Moubaraki and Guy N. L. Jameson
Dalton Trans., 2015, DOI: 10.1039/C4DT03184A

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Dalton Transactions Blog

Archive for the ‘News’ Category

March’s HOT articles

A Cagey Conundrum

Mercury-grabbing ionic liquids hit the gas

A collection of papers in memory of Lord Jack Lewis

February’s HOT articles

Bridging the gap – small ligands in MOFs

January’s HOT articles

Hierarchical functionality in MOF structures

December’s HOT articles

Molecular Memory in a Long-Lasting Mixed Spin State Fe(III) Complex

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