Chemical Communications Blog

HOT ChemComm articles for November

18 Dec 2018

All of the referee-recommended articles below are free to access until Friday 18th January.

Naphthalene and perylene diimides – better alternatives to fullerenes for organic electronics?
Agnieszka Nowak-Król, Kazutaka Shoyama, Matthias Stolteb and Frank Würthner
Chem. Commun., 2018, 54, 13763-13772
DOI: 10.1039/C8CC0764OE, Highlight

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A single-atom Fe–N4 catalytic site mimicking bifunctional antioxidative enzymes for oxidative stress cytoprotection
Wenjie Ma, Junjie Mao, Xiaoti Yang, Cong Pan, Wenxing Chen, Ming Wang, Ping Yu, Lanqun Mao and Yadong Li
Chem. Commun., 2019, Advance Article
DOI: 10.1039/C8CC08116F, Communication

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Si(bzimpy)2 – a hexacoordinate silicon pincer complex for electron transport and electroluminescence
Margaret Kocherga, Jose Castaneda, Michael G. Walter, Yong Zhang, Nemah-Allah Saleh, Le Wang, Daniel S. Jones, Jon Merkert, Bernadette Donovan-Merkert, Yanzeng Li, Tino Hofmann and Thomas A. Schmedake
Chem. Commun., 2018, 54, 14073-14076
DOI: 10.1039/C8CC07681B, Communication

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Maintaining homogeneity during a sol–gel transition by an autocatalytic enzyme reaction
Santanu Panjaa and Dave J. Adams
Chem. Commun., 2019, Advance Article
DOI: 10.1039/C8CC08501C, Communication

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Desferrioxamine:gallium-pluronic micelles increase outer membrane permeability and potentiate antibiotic activity against Pseudomonas aeruginosa
Max Purro, Jing Qiao, Zhi Liu, Morgan Ashcraft and May P. Xiong
Chem. Commun., 2018, 54, 13929-13932
DOI: 10.1039/C8CC08134D, Communication

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Unbalanced MOF-on-MOF growth for the production of a lopsided core–shell of MIL-88B@MIL-88A with mismatched cell parameters
Dooyoung Kim, Gihyun Lee, Sojin Oh and Moonhyun Oh
Chem. Commun., 2019, Advance Article
DOI: 10.1039/C8CC08456D, Communication

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Cram Lehn Pedersen Prize 2019 – call for nominations

28 Nov 2018

By Chris Harding, Development Editor.

The International Committee of the International Symposium on Macrocyclic and Supramolecular Chemistry is pleased to invite nominations for the Cram Lehn Pedersen Prize for young supramolecular chemists.

The Cram Lehn Pedersen Prize, named in honour of the winners of the 1987 Nobel Prize in Chemistry, recognises significant original and independent work in supramolecular chemistry.

Previous winners include Rafal Klajn, Tom F. A. de Greef, Ivan Aprahamian, Feihe Huang, Oren Schermann, Tomoki Ogoshi, Jonathan Nitschke, and Amar Flood.

Those who are within 10 years of receiving their PhD on 31st December 2018 are eligible for the 2019 award. The winner will receive a prize of £2000 and free registration for the ISMSC meeting in Lecce, Italy. In addition to giving a lecture at ISMSC, a short lecture tour will be organized after the meeting in consultation with the Editor of Chemical Communications, the sponsor of the award.

Nomination Details:

Please send your CV, list of publications (divided into publications from your PhD and postdoc and those form your independent work), and if desired, letter of support, or these materials for someone you wish to nominate to Prof. Roger Harrison (ISMSC Secretary) at roger_harrison@byu.edu by 31^st December 2018.

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Shrinking the Size of Hydrogen Evolution Catalysts by Carbon Coating

20 Nov 2018

By Tianyu Liu.

Hydrogen gas is a zero-emission energy resource promising to replace diminishing fossil fuels. The electrolysis of water is a sustainable way to acquire hydrogen gas, but this non-spontaneous process demands electricity to proceed. Therefore, hydrogen evolution reaction (HER) catalysts are used to reduce the energy cost or overpotential of the electrolysis.

Researchers are pursuing ultrafine nanoparticles as HER catalysts due to their high catalytic activity. For example, the HER catalytic activities of Ru nanoparticles are reportedly 100-200% higher than those of bulk Ru catalysts. Unfortunately, the preparation of well-dispersed nanoparticles is challenging because nanoparticles are prone to aggregate together.

Recently in ChemComm, Fuqiang Chu, Yong Qin and coworkers from Changzhou University, China addressed the challenge. They utilized a Ru-based coordination complex and cyanuric acid as the reactants, and synthesized high-performance HER catalysts composed of ~2 nm Ru nanoparticles uniformly dispersed on graphene sheets. During the thermal annealing step in the synthesis, the ligands of the complex and the cyanuric acid both decompose to nitrogen-doped carbon shells covering the as-formed Ru nanoparticles. These shells serve as spacers that prevent particle aggregation (Figure 1).

Figure 1. An illustration of the synthesis of carbon-coated Ru ultrafine nanoparticles on graphene sheets. Tris(2,2′-bipyrindine) ruthenium dichloride is the precursor of the Ru nanoparticles.

In both the acidic and the alkaline electrolytes, the 2 nm Ru particles (RuNC-2) display lower overpotentials and higher current densities than the 5 nm Ru particles (Figure 2) without the carbon coating (RuNC-5). Remarkably, the 2 nm particles showed comparable performance to the benchmark Pt catalyst in the acidic electrolyte (the red and black curves in Figure 2a).

Figure 2. Linear sweep voltammograms of ~3 nm Pt nanoparticles (PtNC), 2 nm Ru nanoparticles (RuNC-2) and 5 nm Ru nanoparticles (RuNC-5) in (a) 0.5 M H₂SO₄ and (b) 1 M KOH aqueous solutions.

The concept of the in-situ generation of protective coatings could inspire the synthesis of other ultra-small nanoparticles to potentially push the HER catalytic performance to new heights.

To find out more please read:

An Ultrafine Ruthenium Nanocrystal with Extremely High Activity for the Hydrogen Evolution Reaction in Both Acidic and Alkaline Media

Yutong Li, Fuqiang Chu, Yang Liu, Yong Kong, Yongxin Tao, Yongxin Li and Yong Qin

Chem. Commun., 2018, DOI: 10.1039/c8cc08276f

About the blogger:

Tianyu Liu obtained his Ph.D. (2017) in Chemistry from University of California, Santa Cruz in the United States. He is passionate about scientific communication to introduce cutting-edge research to both the general public and scientists with diverse research expertise. He is a blog writer for Chem. Commun. and Chem. Sci. More information about him can be found at http://liutianyuresearch.weebly.com/.

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HOT ChemComm articles for October

07 Nov 2018

By Rebecca Withers.

All of the referee-recommended articles below are free to access until 7th December 2018.

Essential but sparse collagen hydroxylysyl post-translational modifications detected by DNP NMR
Wing Ying Chow, Rui Li, Ieva Goldberga, David G. Reid, Rakesh Rajan, Jonathan Clark, Hartmut Oschkinat, Melinda J. Duer, Robert Hayward and Catherine M. Shanahan
Chem. Commun., 2018,54, 12570-12573
DOI: 10.1039/C8CC04960B, Communication

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Rapid synthesis of Co3O4 nanosheet arrays on Ni foam by in situ electrochemical oxidization of air-plasma engraved Co(OH)2 for efficient oxygen evolution
Wenling Gu, Liuyong Hu, Xiaoqing Zhu, Changshuai Shang, Jing Li and Erkang Wang
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC06399K, Communication

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Modification of amine-cured epoxy resins by boronic acids based on their reactivity with intrinsic diethanolamine units
Yumiko Ito, Jumpei Kida, Daisuke Aoki and Hideyuki Otsuka
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC07412G, Communication

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3-Homoacyl coumarin: an all carbon 1,3-dipole for enantioselective concerted (3+2) cycloaddition
Yi-Ru Chen, Madhusudhan Reddy Ganapuram, Kai-Hong Hsieh, Kai-Han Chen, Praneeth Karanam, Sandip Sambhaji Vagh, Yan-Cheng Liou and Wenwei Lin
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC07271J, Communication

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Coinage metal complexes of NHC-stabilized silyliumylidene ions
Philipp Frisch and Shigeyoshi Inoue
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC07754A, Communication

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An ultrafine ruthenium nanocrystal with extremely high activity for the hydrogen evolution reaction in both acidic and alkaline media
Yutong Li, Fuqiang Chu, Yang Liu, Yong Kong, Yongxin Tao, Yongxin Li and Yong Qin
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC08276F, Communication

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Copper A3 Coupling using a Switchable Homogeneous/Heterogeneous Catalyst

06 Nov 2018

By Zoë Hearne.

A MOC, I learned this week, is a metal-organic cage. I was familiar with MOMs, MOFs and MOBs, but MOCs were a new one. A MOM (metal-organic material) is a coordination-driven assembly constructed from metal nodes linked by organic ligands. MOMs encompass both MOFs (metal-organic frameworks) and MOCs (metal-organic cages). A MOF is an extended network with the potential for inner porosity, and a MOC is a discrete metal-ligand cluster. And that’s just about as far down the nomenclature rabbit hole I’m willing to go. If you’re keeping up you’ll realise that I forgot one! A MOB is a crowd of graduate students competing for free coffee at the public seminar.

Dong and co-workers at Shandong Normal University designed and prepared a MOM catalyst constructed from copper(II) nodes and a tripodal ligand consisting of a phenylic wheel functionalised with diketones. In chloroform these two components arrange into discrete MOC assemblies containing two tripodal ligands and three copper ions. The copper ions in the cluster are each coordinated to two diketone moieties (in a acetylacetonate-like fashion) in a quasi-square planar arrangement.

Synthesis of the tripodal ligand functionalised with diketone coordinating moieties.

An interesting property of the material is that it can switch between the MOC form, soluble in halogenated solvents, and an insoluble MOF that assembles upon addition of 1,4-dioxane. 1,4-Dioxane is both an anti-solvent and a ligand; coordination between copper and 1,4-dioxane binds the discrete MOC cages to each other, arranging them into the extended MOF structure. This behaviour can be exploited to prepare a practical catalyst that combines the benefits of both homogeneous and heterogeneous catalysis, namely that homogeneous catalysts are generally more efficient, selective and easier to study, but heterogeneous catalysis are easier to recover and recycle. What better way to solve this problem than with a catalyst that is homogeneous during the reaction conditions, but heterogeneous when it comes to product separation?

Reversible metal-organic cage MOC(top left)-MOF(top right) metal-organic framework transition mediated by the addition of 1,4-dioxane. Coordination bonds between 1,4-dioxane shown (bottom image).

Reversible MOC(top left)-MOF(top right) transition mediated by the addition of 1,4-dioxane. Coordination bonds between 1,4-dioxane shown (bottom image).

The authors used the A³ coupling reaction to demonstrate this concept in a catalytic reaction. The A³ reaction is a transition metal-catalysed, multi-component coupling reaction between aldehydes, alkynes and amines. The products are propargylamines, practical synthetic intermediates for the synthesis of nitrogen heterocycles. The A³ reaction has been extensively studied and can be effected by a wide range of transition metal catalysts. Its versatility makes it a popular choice as a model catalytic reaction to demonstrate innovative ideas in catalytic design – as the authors have done here.

Coordination-driven assemblies have a unique potential for the synthesis of differentially soluble materials, used by the authors for novel catalytic design. Whether this particular metal-ligand combination can be applied to other copper catalysed reactions remains to be seen, nevertheless the principle offers an innovative approach that augments the range of methods striving to bridge the gap between homogeneous and heterogeneous catalysis.

To find out more please read:

Cu₃L₂ metal-organic cages for A³-coupling reactions: reversible coordination interaction triggered homogeneous catalysis and heterogeneous recovery

Gong-Jun Chen, Chao-Qun Chen, Xue-Tian Li, Hui-Chao Ma and Yu-Bin Dong.
Chem. Commun., 2018, 54, 11550-11553
DOI: 10.1039/c8cc07208f

About the author

Zoë Hearne is a PhD candidate in chemistry at McGill University in Montréal, Canada, under the supervision of Professor Chao-Jun Li. She hails from Canberra, Australia, where she completed her undergraduate degree. Her current research focuses on transition metal catalysis to effect novel transformations, and out of the lab she is an enthusiastic chemistry tutor and science communicator.

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The Birth of a Semiconducting Metal Organic Framework by Sulfur Coordination

22 Oct 2018

By Tianyu Liu.

Metal organic frameworks (MOFs) are crystalline nanomaterials composed of metal ions or clusters coordinated with organic ligands. Owing to the versatility of their building blocks, MOFs have multiple functionalities and can serve as gas separators, sensors, catalysts, electrode materials etc. Now the structure diversity of MOFs is further enriched by Wu and coworkers from Soochow University, China. Specifically, the researchers synthesized a semiconducting MOF with tetra-coordinated sulfur units. This breakthrough was recently published in ChemComm.

The uniqueness of the synthesized semiconducting MOF (MCOF-89) is its square-planar tetra-coordinated metal-sulfur structure, which is observed in MOFs for the first time. It was believed that putting a sulfur atom next to a metal node of MOFs was extremely difficult, because of the large discrepancy in bonding energy between metal-sulfur bonds and conventional metal-carboxylate bonds. Incorporating sulfur atoms thereby could undermine the structural stability of MOFs.

The authors addressed this challenge by designing a tetra-coordination environment as illustrated in Figure 1. The four manganese-sulfur bonds effectively reinforced the unstable S coordination. MCOF-89 was synthesized via a solvothermal reaction with Mn(CH₃COO)₂ and thiourea as the Mn and S sources, respectively.

Figure 1. The structure of MCOF-89. The illustration on the left is a three-dimensional lattice structure (the red, green and yellow balls represent oxygen, manganese and sulfur), and the structure on the right shows the Mn-S square-planar tetra-coordination configuration (M = manganese).

The synthesized S-incorporated MOF is a semiconductor with a bandgap of 2.82 eV. Additionally, this MOF is photoactive and is able to generate a photocurrent of ~1.9 µA/cm² upon light irradiation.

This work exemplifies how molecular design can lead to the discovery of novel MOFs with extraordinary structures. It could also inspire other synthesis protocols toward various metal-chalcogenide-containing MOFs with unexpected properties.

To find out more please read:

A Semiconducting Metal-Chalcogenide–Organic Framework with Square-Planar Tetra-Coordinated Sulfur

Huajun Yang, Min Luo, Zhou Wu, Wei Wang, Chaozhuang Xue and Tao Wu

Chem. Commun., 2018, 54, 11272-11275

About the blogger:

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HOT ChemComm articles for September

04 Oct 2018

By Rebecca Withers.

All of the referee-recommended articles below are free to access until 4th November 2018.

Organocatalytic decarboxylative alkylation of N-hydroxy-phthalimide esters enabled by pyridine-boryl radicals
Liuzhou Gao, Guoqiang Wang, Jia Cao, Dandan Yuan, Cheng Xu, Xuewen Guo and Shuhua Li
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC06152A, Communication

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A new C,N-cyclometalated osmium(II) arene anticancer scaffold with a handle for functionalization and antioxidative properties
Enrique Ortega, Jyoti G. Yellol, Matthias Rothemund, Francisco J. Ballester, Venancio Rodríguez, Gorakh Yellol, Christoph Janiak, Rainer Schobert and José Ruiz
Chem. Commun., 2018,54, 11120-11123
DOI: 10.1039/C8CC06427J, Communication

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Descriptors of magnetic anisotropy revisited
Mauro Perfetti and Jesper Bendix
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC05756G, Communication

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A semiconducting metal-chalcogenide–organic framework with square-planar tetra-coordinated sulfur
Huajun Yang, Min Luo, Zhou Wu, Wei Wang, Chaozhuang Xue and Tao Wu
Chem. Commun., 2018,54, 11272-11275
DOI: 10.1039/C8CC06997B, Communication

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Transition between tangential and co-axial liquid crystalline honeycombs in the self-assembly of Y-shaped bolapolyphiles
Anne Lehmann, Marko Prehm, Changlong Chen, Feng Liu, Xiangbing Zeng, Goran Ungar and Carsten Tschierske
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC06281A, Communication

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Unraveling the isomeric heterogeneity of glycans: ion mobility separations in structures for lossless ion manipulations
Gabe Nagy, Isaac K. Attah, Sandilya V. B. Garimella, Keqi Tang, Yehia M. Ibrahim, Erin S. Baker and Richard D. Smith
Chem. Commun., 2018, Advance Article
DOI: 10.1039/C8CC06966B, Communication

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ChemComm Emerging Investigator Lectureship – nominations now open!

02 Oct 2018

By Rebecca Withers.

Know an outstanding emerging scientist who deserves recognition? Nominate now for the 2019 ChemComm Emerging Investigator Lectureship

We are pleased to welcome nominations for the 2019 Emerging Investigator Lectureship for ChemComm.

All nominations must be received by Friday 25th January 2019.

ChemComm Emerging Investigator Lectureship
• Recognises emerging scientists in the early stages of their independent academic career.
• Eligible nominees should have completed their PhD on or after the 15th September 2010.

Lectureship details
• The recipient of the lectureship will be invited to present a lecture at three different locations over a 12-month period, with at least one of these events taking place at an international conference.
• The recipient will receive a contribution of £1500 towards travel and accommodation costs for their lectures, as well as a certificate.
• The recipient will be asked to contribute a review article for the journal.

How to nominate
Self-nomination is not permitted. Nominators must send the following to the editorial team via chemcomm-rsc@rsc.org by Friday 25th January 2019.
• Recommendation letter, including the name, contact details and website URL of the nominee.
• A one-page CV for the nominee, including a summary of their education, dates of key career achievements, a list of up to five of their top independent publications, total numbers of publications and patents, and other indicators of esteem, together with evidence of career independence.
• A copy of the candidate’s best publication to date (as judged by the nominator).
• Two supporting letters of recommendation from two independent referees. These should not be someone from the same institution or the candidate’s post doc or PhD supervisor.

The nominator and independent referees should comment on the candidate’s presenting skills.

Incomplete nominations or those not adhering to the above requirements will not be considered, and nominees will not be contacted regarding any missing or incorrect documents.

Selection procedure
• The editorial team will screen each nomination for eligibility and draw up a shortlist of candidates based on the nomination documents provided.
• Shortlisted candidates will be asked to provide a brief supporting statement summarising their key achievements, highlighting the impact of their work and justifying why they deserve the specific lectureship for which they have been entered.
• The recipient of the lectureship will then be selected and endorsed by a selection panel composed of members of the ChemComm Editorial Board. The winner will be announced in the first half of 2019.

NB: Please note that members of the selection panel from the ChemComm Editorial Board are not eligible to nominate, or provide references, for this lectureship.

For any queries, please contact the editorial team at chemcomm-rsc@rsc.org.

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How do Anions Fight Indoor Organic Contaminants?

24 Sep 2018

By Tianyu Liu.

Indoor air quality is critical to public health. Chronic exposure to indoor organic contaminants (IOCs), including aldehydes and benzene homologues, substantially increases the risk of having respiratory diseases. In recent years, negative air ions (NAIs) have emerged as promising materials to decompose IOCs. NAIs are negatively charged ions generated via ionizing air. However, the limited understanding of the decomposition reaction mechanisms hinders the safety evaluation and wide adoption of NAI-cleaning.

A group of Chinese researchers led by Jin-Ming Lin of Tsinghua University recently demonstrated in ChemComm a powerful tool to unveil the reaction mechanisms. They built a system integrated with an NAI generator, an IOC sprayer and a mass spectrometer (Figure 1). NAIs containing mostly CO₃^– were produced by the ionization of air. These anions then mixed and reacted with the sprayer-delivered IOCs in front of the mass spectrometer inlet. All species generated during the reactions were directly brought into the mass spectrometer by inert N₂ for characterization.

Figure 1. The experimental set-up of the integrated system.

This device revealed real-time reaction kinetics by identifying the reaction intermediates. The mass spectrum of a common IOC, formaldehyde, when reacted with CO₃^– is presented in Figure 2a. Two pronounced peaks with mass to charge ratios (m/z) of 45.10 and 60.10 were assigned to HCOO^– and CO₃^–, respectively. Additionally, the 45.10 peak was only detected when formaldehyde was present (Figure 2b). On the basis of these observations, the authors concluded that the major pathway of formaldehyde degradation by CO₃^–was the reaction between CO₃^– and the α-H atom of the aldehyde group. With identical instrumentation, the authors also proposed how the reactions between CO₃^– and benzene homologues or esters may proceed.

Figure 2. (a) The mass spectrum of reaction intermediates between CO₃^– and 10 ppm formaldehyde. (b) The change of peak intensities of m/z = 60.10 and 45.10 peaks with the operation time. Formaldehyde was present during 7.0-14.0 min.

The results obtained by this study could greatly deepen the understanding of NAI-based chemistry. It could also be useful to investigate kinetics of a broad range of other chemical reactions involving charged reactants.

To find out more please read:

Real-Time Characterization of Negative Air Ion-Induced Decomposition of Indoor Organic Contaminants by Mass Spectrometry

Ling Lin, Yu Li, Mashooq Khan, Jiashu Sun and Jin-Ming Li

Chem. Commun., 2018, DOI: 10.1039/c8cc05795h

About the blogger:

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EuroBIC 14

10 Sep 2018

By Rebecca Withers.

This August saw the occasion of the 14th European Biological Inorganic Chemistry Conference (EuroBIC), held at the University of Birmingham in the UK. With an excellent line up of internationally renowned plenary and keynote speakers the event was a huge success, attracting around 400 attendees.

The Royal Society of Chemistry was pleased to support the event, offering poster prizes of books and book vouchers. The winners of RSC vouchers were:

Raul Berrocal-Martin (University of Glasgow) – Dalton Transactions Poster Prize
Wilma Neumann (Massachusetts Institute of Technology) – Metallomics Poster Prize
Ying Zhou (University of Hong Kong) – ChemComm Poster Prize
Leon Jenner (University of East Anglia) – Chemical Science Poster Prize

The following presenters also won the RSC Highly Commended Poster Awards:

Gloria Vigueras Bautista (University of Murcia)
Nicolai Burzlaff (Friedrich-Alexander University)
Samya Banerjee (University of Warwick)
Riccardo Bonsignore (Cardiff University)
Philip Ash (University of Oxford)

Dalton Transactions associate editor Nils Metzler-Nolte (Ruhr-Universität Bochum) and Chemical Science assistant editor William King were on hand to award the prizes.


Raul Berrocal-Martin (left) receiving the Dalton Transactions prize from Nils Metzler-Nolte (right)	Ying Zhou (left) receiving the ChemComm prize from Nils Metzler-Nolte (right)

Leon Jenner (left) receiving the Chemical Science prize from William King (right)	Gloria Vigueras Bautista (left) receiving a Highly Commended Poster Prize from William King (right)

Riccardo Bonsignore (left) receiving a Highly Commended Poster Prize from William King (right)	Philip Ash (left) receiving a Highly Commended Poster Prize from William King (right)