Author Archive

Jumping Crystals

Posted on behalf of Josh Campbell, web writer for CrystEngComm 

The phenomenon of jumping crystals was first reported in 1983 when it was discovered that heating crystals of (phenylazophenyl)palladiumhexafluoroacetylacetonate caused not only a polymorphic transition, but also the sample to literally “jump” off the heat source.  Since then, mechanically responsive materials research has blossomed due to potential applications in medical devices, actuators and electronic sensors. Most research in the field has focussed on molecular scale movement (typically using rotaxanes or catenanes) or light-activated polymers for macroscopic movement. However, single crystals possess many of the properties needed for practical applications of actuators.  The ordered structure of the crystal should allow any induced effect to travel faster which allows faster energy transfer, shorter response times and faster recovery. 

Light- and heat-induced mechanical effects in single crystalsA new highlight article in CrystEngComm recaps some of the recent progress in the field, focusing on the mechanical processes seen in thermo- and photo-responsive crystals. Thermally induced jumping is known as the thermosalient effect and has been reported for many materials. Crystals that exhibit this effect generally fall into three types: crystals which contain hydrogen bonds; crystals without hydrogen bonding groups that form stacked layers; and crystals with no strong intermolecular interactions whatsoever. For the second class, the ability of a layered structure to exhibit hopping depends on the interactions between layers and the thermal motion of the atoms between them. Oxitropium bromide is one such crystalline material, which undergoes a reversible conformational change which has the effect of loading, and then decompressing, a spring. For polar molecules, a compression along the most polar axis can lead to mechanical effects. 

Photo-responsive crystals rely on the photochromic effect, a reversible transformation that occurs on the absorption of electromagnetic radiation. Crystals can respond mechanically to this absorption with a range of mechanical effects. For example, microcrystals of trans-4-aminoazobenzene bend away from UV light. Bending and curling is often seen with cis–trans isomerism, ring opening and closure and cycloaddition reactions. The photosalient effect has also been reported, whereby mechanical strain develops in the crystal due to a photochemical reaction. An example of this is α-santonin, its crystals turn yellow and burst when exposed to sunlight. 

Research into thermal and photo induced mechanical effects is now picking up compared to previous decades after the realisation of their importance in both energy conversion and for developing mechanically responsive materials. 

Read the article now for more details: 

Thermally induced and photoinduced mechanical effects in molecular single crystals—a revival 

N. K. Nath, M. K. Panda, S. C. Sahooa and P. Naumov
CrystEngComm, 2014, DOI: 10.1039/C3CE41313F 


Josh Campbell Josh Campbell is a PhD student, currently at the University of Southampton, UK studying crystal structure prediction of organic semiconductors. He received his BSc from the University of Bradford.
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CrystEngComm Editor’s choice

In this Editor’s choice post, Professor Christer Aakeröy, Associate Editor for CrystEngComm, talks about his favourite articles published in the journal in recent months. Christer has chosen the most interesting articles in the area of molecular recognition crystal engineering.  


Deprotonation of resorcinarenes by mono- and diamine bases: Complexation and intermolecular interactions in the solid state
N. Kodiah Beyeh,   Arto Valkonen and  Kari Rissanen 
CrystEngComm, 2013, DOI: 10.1039/C3CE42291G    

Structural chemistry investigations of macrocyclic compounds such as calixarenes and resorcinarenes are frequently hampered due to problems with crystal growth, and it is quite rare that a successful structural study is supported and complemented by solution- and gas-phase data.  Rissanen and co-workers have produced a systematic and comprehensive exploration of several deprotonated alkyl-resorcinarenes which offers a broad perspective of the structural and chemical behavior of representatives of a ‘classic’ supramolecular system.  The single-crystal studies indicate that the deprotonated macrocycles act as effective hosts for the protonated amines in the solid state and the acid-base behavior in solution is monitored by NMR titrations.  The deprotonated resorcinarenes (monomer and dimer) were observed using EI mass spectrometry in negative ion mode while the 1:1 and 2:1 complexes with the protonated guests were observed in positive ion mode in the gas phase.    

c3ce42291g   

 

Can self-assembly of copper(II) picolinamide building blocks be controlled?
Marijana Đaković, Diogo Vila-Viçosa, Nuno A. G. Bandeira, Maria José Calhorda, Bojan Kozlevčar, Zvonko Jagličić and Zora Popović 
CrystEngComm, 2013, 15, 8074-8087   

In this paper, Đaković et al examine the structural role played by picolinamide ligands in the directed assembly of a series of Cu(II) based complexes.   The study is supported by an impressive range of experimental and theoretical tools, and offers a comprehensive analysis and evaluation of an important aspect of crystal engineering.    The authors have examined the precise role that different factors play in the assembly of each structural motif and the outcome is a much enhanced understanding of the templating effect of the metal ion as well as of the complementarity of non-covalent interactions.  Finally, the structural work is supported by careful magnetic measurements the results of which are subsequently properly interpreted and rationalized using DFT-based calculations.   

Copper complexes self-assembly   

 

Knowledge-based hydrogen bond prediction and the synthesis of salts and cocrystals of the anti-malarial drug pyrimethamine with various drug and GRAS molecules
Amit Delori, Peter T. A. Galek, Elna Pidcock, Mohit Patni and William Jones 
CrystEngComm, 2013,15, 2916-2928   

The ability to determine which primary intermolecular interactions are most likely to take place given the presence of certain functional groups is of key importance in crystal engineering.  In this study, the authors adopt a knowledge-based approach that takes full advantage of the unique structural information that is provided within the Cambridge Structural Database.  Through the use of hydrogen bond propensity calculations (HBPC), which perform a statistical analysis of the occurrence of specific hydrogen bonds among structures of relevant molecules, it is possible to estimate which hydrogen bonds are most likely to take place between different molecules.   Different hydrogen bonds are assigned propensity scores which provides an avenue for predicting of co-crystals are likely to form between two different molecules and, if so, the type of intermolecular interactions that can be expected within the heteromeric co-crystal.  HBPC calculations were utilized to predict the likelihood of forming co-crystals between the anti-malarial drug pyrimethamine and carbamazepine, theophylline, aspirin, α-ketoglutaric acid, saccharin, coumaric acid, succinimide and L-isoleucine.  The HBPC agreed with the experimental observations indicating that this approach may offer effective and versatile tools for finding new solid forms of high-value chemicals such as pharmaceuticals and agrochemicals.   

H-bond prediction in pyrimethamine synthesis   

 

Complexities of mechanochemistry: elucidation of processes occurring in mechanical activators via implementation of a simple organic system
Adam A. L. Michalchuk, Ivan A. Tumanov and Elena V. Boldyreva 
CrystEngComm, 2013,15, 6403-6412   

Mechanochemistry is a current ‘hot topic’ which is of considerable interest to both covalent and supramolecular synthetic chemists.  A wide range of chemical transformations are now known to be possible using essentially ‘green’ reaction conditions.  Arguably, most papers that have presented in this field focus on proof-of-principle studies which demonstrate that “functional group ‘A’ can be converted to ‘B’ using the following reaction conditions”, but mechanistic or kinetic studies are still relatively uncommon.  In this paper, however,  Michalchuk et al, present a very detailed examination of the α-glycine : b-malonic acid system which include an analysis of how two key mechanical ‘forces’ – impact and shear – can influence reaction paths and product distribution.  This study clearly demonstrate that what actually happens in a ball mill or through a mortar-pestle treatment is likely to be far more complicated than what is assumed in most studies, notable the role played by the actual mechanoreactor itself.  The results are likely to be of critical importance to many mechanochemical reactions especially in the context of scale-up.   

Mechanochemistry    

 

Synthon identification in co-crystals and polymorphs with IR spectroscopy. Primary amides as a case study
Arijit Mukherjee, Srinu Tothadi, Shaunak Chakraborty, Somnath Ganguly and Gautam R. Desiraju 
CrystEngComm, 2013, 15, 4640-4654

It is probably fair to say that many crystal engineering efforts rely far too heavily on the use of single-crystal X-ray diffraction for product analysis and/or for interpreting the outcome of a particular crystallization or supramolecular synthesis.  However, in this paper, Desiraju and co-workers present a careful and informative study that correlates crystallography with vibrational spectroscopy.  In order to overcome the well-known challenges when using IR spectroscopy for analyzing polymorphs and co-crystals containing multiple synthons, the authors have employed a four-step approach that relies on the use of ‘spectral markers’ that can be directly associated with bonds in specific synthons.  The method is tested on an acid–phenol–pyridine co-crystal system and subsequently utilized for correctly identifying the different synthons in polymorphs of isonicotinamide.        

Synthons 

 

Halogen bond directionality translates tecton geometry into self-assembled architecture geometry
Marco Saccone, Gabriella Cavallo, Pierangelo Metrangolo, Andrea Pace, Ivana Pibiri, Tullio Pilati, Giuseppe Resnati and Giancarlo Terraneo 
CrystEngComm, 2013,15, 3102-3105 

This paper offers a particularly well-planned and carefully executed strategy for supramolecular synthesis.  One some level, this study may seem overly simplistic and the results may appear to be ‘obvious’ but this is, in my opinion, a testament to the progress that has been made in this field.  We sometimes forget that non-covalent synthesis has to rely on relatively weak and reversible interactions in an environment where solvent molecules are more than capable of disrupting solute-solute biding and, furthermore, that recrystallization is generally favored over heteromeric co-crystallizations.  The fact that we may think that the results presented herein are unsurprising simply means that we are making considerable progress towards finding and developing supramolecular reactions that display a robustness and reliability that we typically associate with named reactions in organic synthesis. 

Halogen bonds.   

 

 


ChristerAakeroy

Prof. Christer Aakeröy is a University Distinguished Professor at Kansas State University, Manhattan, KS, USA.  He is broadly interested in examining the way in which molecules recognize and bind to each other, and how they communicate and assemble into (occasionally) functional architectures.  He is currently the Chair of the Board of Governors for the Cambridge Crystallographic Data Centre and is an Associate Editor for CrystEngComm.

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Hongjie Zhang elected to the Chinese Academy of Sciences

Hongjie ZhangWe are delighted to announce that Hongjie Zhang, Associate Editor for CrystEngComm, has been selected to be an academician of the faulty of chemistry of the Chinese Academy of Sciences (CAS). Hongjie is the Deputy Director of the Changchun Institute of Applied Chemistry and has been an Associate Editor for CrystEngComm since 2013 – See last year’s blog post.

Selection for the title of academician is the highest academic honour in the field of science and technology in China and is based on significant academic achievement and scientific contribution over a sustained career. Hongjie was elected alongside 52 other new domestic members and 8 international members, including the 2004 Nobel chemistry laureate Aharon Ciechanover, at a ceremony in Beijing last month.

Prof. Hongjie Zhang received his PhD in Solid State Chemistry and Material Sciences at Universite de Bordeaux I, Laboratoire de Chimie du Solide du CNRS (France) in 1993. He joined Changchun Institute of Applied Chemistry, CAS, as a professor in 1994. His current research interests involve lanthanide organic–inorganic hybrid materials, electroluminescent devices, functional nanomaterials and the structure and properties of rare earth magnesium alloys. He has published over 350 papers in peer-reviewed international journals.

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CrystEngComm celebrates crystallography in 2014

Posted on behalf of Jamie Humphrey, Editor

CrystEngComm2014Crystallography is a core science, underpinning many areas of research, and central to crystal engineering. 2014 marks the centenary of the birth of X-ray crystallography and has been proclaimed the International Year of Crystallography. We are delighted to celebrate this important science in CrystEngComm in a number of ways in 2014.

Our celebrations will take the form of the publication of four themed issues dedicated to the best crystal engineering research from four key geographical regions. Keep an eye out for these issues, which will appear throughout the year, covering India (Guest Editor: Professor Rahul Banerjee, CSIR-National Chemical Laboratory, Pune, India), Europe (Guest Editors: Professor Dario Braga, University of Bologna, Italy and Professor Michaele Hardie, University of Leeds, UK), the Americas (Guest Editors: Professor Christer Aakeröy, Kansas State University, USA and Professor Tomislav Friščić, McGill University, Canada) and Asia-Pacific (Guest Editors: Professor Stuart Batten, Monash University, Australia and Professor Jagadese Vittal, National University of Singapore, Singapore).

We also have a number of excellent topic-themed issues planned for the year, illustrating the breadth of crystal engineering research: Functional co-crystals (Guest Editor: Professor Colin Pulham, University of Edinburgh, UK), Structural macrocyclic supramolecular chemistry (Guest Editors: Professor Len Barbour, University of Stellenbosch, South Africa, Professor Len MacGillivray, University of Iowa, USA and Professor Kari Rissanen, University of Jyväskylä, Finland), Nanoparticle assemblies (Guest Editors: Professor Marie Paule Pileni, UPMC, Paris, France, Professor P. Davide Cozzoli, Università del Salento & National Nanotechnology Laboratory, Italy and Professor Nicola Pinna, Humboldt-Universität zu Berlin, Germany), and Nanocrystal growth via oriented attachment (Guest Editors: Dr R. Lee Penn, University of Minnesota, USA, Dr Hengzhong Zhang, University of California, Berkeley, USA, Dr Zhang Lin, State Key Laboratory of Structural Chemistry, China and Dr Helmut Cölfen, University Konstanz, Germany). These follow the themed issues published in 2013, details of which are in Table 1.

Table 1 2013 themed issues, representing the breadth of crystal engineering


Themed issue Guest editor(s)
Covalent organic frameworks Andy Cooper, University of Liverpool, UK
Crystallisation: from fundamentals to application Alastair Florence, University of Strathclyde, UK
Halogen bonding: from self-assembly to materials and biomolecules William T Pennington, Clemson University, USA
Giuseppe Resnati, Politecnico di Milano, Italy
Mark S Taylor, University of Toronto, Canada
MOFs George Shimizu, University of Calgary, Canada
Rahul Banerjee, CSIR-National Chemical Laboratory, India
Miao Du Tianjin, Normal University, China
NMR crystallography John Ripmeester, National Research Council, Canada
Roderick E. Wasylishen, University of Alberta, Canada

 

Continuing the International Year of Crystallography celebrations, the Royal Society of Chemistry, in partnership with Calcutta University, Jadavpur University and IISER-Kolkata, will organise a symposium on structural chemistry in November in India. We will also participate in a global experiment for school children involving crystals. Keep an eye out for more information about the symposium and the global experiment as they develop.

In 2013 a number of people joined our Editorial Board, bringing with them expertise and experience of their particular research fields. Joining Editorial Board Chair, Len MacGillivray (University of Iowa, USA), Associate Editors Rahul Banerjee (CSIR-National Chemical Laboratory, India) and Christer Aakeröy (Kansas State University, USA) and Board member Nicola Pinna (Humboldt-Universität zu Berlin, Germany) are Associate Editors Hongjie Zhang (Changchun Institute of Applied Chemistry, China) and Georg Garnweitner (TU Braunschweig, Germany) and Board members Graeme Day (University of Southampton, UK), Tomislav Friščić (McGill University, Canada), Michaele Hardie (University of Leeds, UK), Helmut Cölfen (Universitat Konstanz, Germany) and Pierangelo Metrangolo (Politecnico di Milano, Italy). We very much look forward to our collaborations with them all.

The way we connect with our friends, peers and colleagues is changing, and social media is an important tool for this. CrystEngComm is no different. We have a number of outlets for CrystEngComm via social media, expanding the ways in which people can get involved with the journal. The journal has a Facebook page and Twitter account (why not join our 1000 followers?) and our LinkedIn group is a good way to learn about relevant conferences and other news. Our latest offering is our ‘Crystal Clear’ Pinterest page, illustrating some of the stunning crystal images that are included in the journal.

Fiona McKenzie (Deputy Editor) and I will be attending two conferences in 2014: the Crystal Engineering Gordon Research Conference and the IUCr meeting. An important related meeting is the Faraday Discussion meeting 170 with a focus on Mechanochemistry: From Functional Solids to Single Molecules. The meeting will be in Montreal, Canada in May, and more details are available via www.rsc.org/ConferencesAndEvents/RSCConferences/FD/FD170/index.asp

We were very pleased to support a number of international conferences in 2013 through sponsorship. We also provide support via poster prizes – in 2013, we awarded 10 poster prizes, celebrating the achievements of members of our community in the early years of their academic careers. If you are organising a conference in 2014 and you would like us to sponsor a poster prize, please let us know.

Let us connect you and your work into the world’s leading chemistry community in 2014, the International Year of Crystallography: publish with CrystEngComm!

Have a fantastic 2014!

Download the pdf here

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