Hot Article – Page 8 – CrystEngComm Blog

Archive for the ‘Hot Article’ Category

Small crystals with big prospects – magnetite composites as candidates for energy storage

29 Jan 2013

In their Hot Article, Qiang Shen and colleagues from Shandong University report the generation of Fe₃O₄–C composites via the evolution of orthorhombic FeOCl. The crystals display some interesting electrochemical properties which make them potential candidates for next generation lithium ion batteries (LIBs).

We use LIBS in portable electronic devices such as phones and computers and LIB development has sparked a great deal of interest among materials scientists and crystal engineers alike.

Take a look at the results of the team’s research by downloading the article below, which is free to access for 4 weeks.

A chemical composition evolution for the shape-controlled synthesis and energy storage applicability of Fe₃O₄–C nanostructures
Fenfen Xu, Wenpei Kang, Xinxin Wang, Rui Liu, Chenhao Zhao and Qiang Shen

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Halogen vs. hydrogen bonding

16 Jan 2013

Competing hydrogen-bond and halogen-bond donors in crystal engineering

In this HOT article by Aakeröy et al, relevant hydrogen-bond and halogen-bond acceptors and donors were selected to study the competition between these two molecular interactions in supramolecular assembly. Twelve co-crystals were synthesized based on two different azobipyridines as acceptors and six donor molecules possessing both hydrogen-bond and halogen-bond moieties. The key conclusions which could be drawn from the study were: (i) the hydrogen-bond is the principal driving force in the formation of 3,3′-azabipyridine co-crystals whereas hydrogen and halogen bonds do indeed compete in the formation of the 4,4′-azabipyridine co-crystals; (ii) the iodine donor appears to be a better halogen-bond donor than bromine; and (iii) the three different hydrogen-bond donors studied (–COOH, –OH and –CN(R)OH) behave similarly.

Releasing the electronic potential in aluminium nitride

13 Dec 2012

Photo of free-standing AlN wafer

The use of aluminium nitride in solid-state optoelectronic devices has been hindered by high defect levels limiting the output power, efficiency and lifetimes of mid-UV LEDs. Now, there is a possible solution, thanks to the method described in this HOT CrystEngComm paper.

R. Radhakrishnan Sumathi from Ludwig Maximilians University reports a physical vapour transport growth method using silicon carbide as a foreign substrate. The result is a more homogeneous structure than afforded by previous methods with uniform levels of defects and impurities across the wafer.

Read more now…

Bulk AlN single crystal growth on foreign substrate and preparation of free-standing native seeds
R. Radhakrishnan Sumathi
CrystEngComm, 2013
DOI: 10.1039/C2CE26599K

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Guanidinium-based building blocks

29 Nov 2012

Guanidinium-based synthons are useful for building ordered supramolecular structures due to their large number of charge-assisted hydrogen bonds (the guanidinium cation has 6 active H bonds). However, due to this plethora of potential intermolecular interactions, it can be a tricky to predict and design resultant structures – which is what crystal engineering is all about…

In their latest CrystEngComm Communication, Yadav and Gorbitz have endeavoured to restrict the modes of hydrogen bonding by substituting with TBD (see below). TBD has only 2 N-H donors which is much more manageable for these purposes! They partnered the TBD with dicarboxylic acid, 2,2′-bipyridine-5,5′ dicarboxylic acid (BPDA) to form a 2:1 complex. Additional acceptor sites at the carboxylate lone pairs means that 4 water molecules can co-crystallise along with the structure, leading to extended water channels or open organic networks containing clusters of water.

Read more now…

A supramolecular 2:1 guanidinium–carboxylate based building block for generation of water channels and clusters in organic materials
Vitthal N. Yadav and Carl Henrik Görbitz
CrystEngComm, 2013, DOI: 10.1039/C2CE26572A

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Polymorphism co-crystal screening

15 Nov 2012

In their HOT article, Jones and co-workers at the University of Cambridge present a comprehensive crystal form screen for the phenazine:mesaconic acid system, employing a variety of different co-crystallisation methods.

: Phenazine:mesaconic acid system

The researchers identified and characterised three anhydrous co-crystal polymorphs, one co-crystal hydrate and one DMSO co-crystal solvate, and also highlighted a novel co-crystallisation technique at the interface between two immiscible solutions, yielding a pure phenazine:mesaconic acid co-crystal form. Traditional solvent-based methods usually used for polymorphism screening were inappropriate for this system due to the large differences in solubility of phenazine and mesaconic acid.

Role of aspartic acid in regulating the growth of common kidney stones

13 Nov 2012

Yu Huang, S. Roger Qiu and colleagues have used in situ atomic force microscopy to investigate how the growth of calcium oxalate monohydrate is inhibited by 6-residue linear aspartic acid peptides.

Analysis of the step speed data showed that the aspartic acid enantiomers block active kink sites through step-pinning.

Calcium oxalate monohydrate is the main inorganic component in the most common types of kidney stones, so preventing their formation is of great clinical importance.

H-bonds under pressure

26 Oct 2012

Crystal growth of aniline-II at 0.8 GPa

In an extension to previous work showing that H-bond lengths are pressure sensitive, Parsons and co-workers used the PIXEL method (a computational method for structural prediction) to study the variation in energy of intermolecular interactions with pressure, in two crystalline phases of aniline.

For aniline II, at a pressure of 7.3 GPa, the pressure-induced shortening of the H-bonds was found to go beyond the Cambridge Structural Database limit with the H-bonds being similar in energy to the CH-π contacts.

This ability to manipulate the hierarchy of intermolecular interactions by high pressure could have potentially important implications in crystal engineering.

Read more for FREE about the use of high pressure in crystalline solids at:

Destabilisation of hydrogen bonding and the phase stability of aniline at high pressure
Nicholas P. Funnell, Alice Dawson, William G. Marshall and Simon Parsons
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE26403J, Paper

You may also want to check out previous work from Simon Parsons:

Alanine at 13.6 GPa and its pressure-induced amorphisation at 15 GPa
Nicholas P. Funnell, William G. Marshall and Simon Parsons
CrystEngComm, 2011, 13, 5841-5848
DOI: 10.1039/C1CE05487B, Paper

The effect of pressure on the crystal structure of L-alanine
Nicholas P. Funnell, Alice Dawson, Duncan Francis, Alistair R. Lennie, William G. Marshall, Stephen A. Moggach, John E. Warren and Simon Parsons
CrystEngComm, 2010, 12, 2573-2583
DOI: 10.1039/C001296C, Paper

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Building MOFs with 3-pyridylisonicotinamide ligands

18 Oct 2012

Robert LaDuca, and colleagues at Michigan State University, have hydrothermally synthesised divalent metal coordination polymers featuring the ligand, 3-pyridylisonicotinamide (3-pina). The 3-pina ligand has a hydrogen bonding donor and acceptor locus at its central amide, making supramolecular structure direction achievable, something that is not possible using the regularly tested ligand, 4,4′-bipyridine.

The 3-pyridylisonicotinamide ligand has a kinked disposition of its nitrogen atoms.

The team discuss 3 very diverse structures featuring the 3-pina ligand, showing that the dimensionality in the resulting coordination polymers very much depends on the metal coordination environment and the sulfate binding mode that occurs in each case.

Download the paper now to find out more:

Metal dependent dimensionality in sulfate coordination polymers containing 3-pyridylisonicotinamide
Jacqueline S. Lucas, Jacob W. Uebler and Robert L. LaDuca
CrystEngComm, 2012
DOI: 10.1039/C2CE26333E, Paper

Take a look at some of the teams other recent CrystEngComm articles:

Topological diversity in zinc coordination polymers with 5-substituted isophthalate and bis(4-pyridylmethyl)piperazine ligands
Amy L. Pochodylo and Robert L. LaDuca
CrystEngComm, 2011,13, 2249-2261
DOI: 10.1039/C0CE00715C, Paper

Metal and ligand binding mode dependent topologies in phthalate coordination polymers with bis(4-pyridylformyl)piperazine co-ligands
Curtis Y. Wang, Zachary M. Wilseck, Ronald M. Supkowski and Robert L. LaDuca
CrystEngComm, 2011,13, 1391-1399
DOI: 10.1039/C0CE00632G, Paper

Cadmium bis(4-pyridylformyl)piperazine coordination polymers: layered nets and a novel 3,5-connected binodal lattice
Jacqueline S. Lucas, Amy L. Pochodylo and Robert L. LaDuca
CrystEngComm, 2010,12, 3310-3317
DOI: 10.1039/C0CE00117A, Paper

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Photodimerization control in the solid state

15 Oct 2012

In an extension of previous work, this HOT Article, by Kraig Wheeler and co-workers describes their attempts to control the regio- and stereochemical outcomes of [2+2] photochemical dimerization in the solid state.

In their 2011, CrystEngComm article, the team reported on the development of a sulfonamidecinnamic acid framework which could be likened to the shape of a fish-hook. Upon crystallisation, the structures form supramolecular dimers where the neighbouring C=C double bonds are oriented mutally co-planar. It is this feature that allows UV initiated dimerisation into the corresponding cyclobutane product.

In their latest CrystEngComm, they extend this study by looking at a greater range of frameworks with different R substituents. To see what impact this has on the supramolecular photodimerisation, download the article now for FREE:

Solid-state photodimerization reactions of racemic and homochiral phenylalanine sulfonamidecinnamic acids
Zhiqing Yan, Andrew J. Bolokowicz, Teage K. Collett, Sarah A. Reeb, Joshua D. Wiseman and Kraig A. Wheeler
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE26307F

Also of interest:
Enantiocontrolled solid-state photodimerizations via a chiral sulfonamidecinnamic acid
Kraig A. Wheeler, Joshua D. Wiseman and Rebecca C. Grove
CrystEngComm, 2011, 13, 3134–3137
DOI: 10.1039/C0CE00516A

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From disorder to order: evidence of stable ion clusters

18 Sep 2012

Evidence for an amorphous to crystalline transition

In this HOT Article, Franca Jones suggests the existence of highly disordered clusters that form prior to crystallization of barite and gypsum, based on Fourier-Transform infra-red (FTIR) spectra of saturated solutions as they crystallize. Jones reports the evolution of various mineral phases prior to the appearance of the crystalline mature product and in the case of barite, shows that the FTIR evidence is strongly supported by electron diffraction. The role of water in the process is also investigated…

Read more for FREE at:

Infrared investigation of barite and gypsum crystallization: Evidence for an amorphous to crystalline transition
Franca Jones
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE25918D

Also of interest may be:

Barium sulfate crystallization dependence on upper rim calix[4]arene functional groups
Andrew Baynton, Mark I. Ogden, Colin L. Raston and Franca Jones
CrystEngComm, 2012, 14, 1057-1062
DOI: 10.1039/C1CE06083J

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