CrystEngComm Blog

Glass ceramics are remarkable materials and as their name suggests, they exhibit properties of both glasses and ceramics. An interesting and well known example of a glass ceramic is the lithium, silicon and aluminium-oxide material which provides the almost unbreakable tops to our electric hobs as well as protection for deep space mirrors.

An SEM micrograph of the polished cross-section of a sample annealed for 20h

This isn’t the only glass ceramic system nor is the low (or even zero) coefficient of thermal expansion the only interesting property these materials have. Glass ceramics containing crystals of the fresnoite type possess interesting piezoelectric, pyroelectric and surface acoustic properties. This Hot Article from Wolfgang Wisniewski, Marek Patschger and Christian Russel reports the Sr-fresnoite surface crystallisation in a 2SrO·TiO₂·2.75 SiO₂ glass and is a great example of modern functionality driven research.

lFind out more about the teams discoveries by downloading their article below for free

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Sr-fresnoite surface crystallisation in a 2SrO•TiO₂•2.75 SiO₂ glass studied by EBSD
Wolfgang Wisniewski, Marek Patschger and Christian Rüssel
CrystEngComm, 2012, Advance Article

Other articles which may also be of interest include:

Composition and texture of barium silicate crystals in fresnoite glass-ceramics by various scanning electron microscopic techniques
Marcus Nagel, Wolfgang Wisniewski, Günter Völksch, Christian Borschel, Carsten Ronning and Christian Rüssel
CrystEngComm, 2011, 13, 3383-3389

Crystallisation of iron containing glass–ceramics and the transformation of hematite to magnetite
Wolfgang Wisniewski, Ruzha Harizanova, Günter Völksch and Christian Rüssel
CrystEngComm, 2011, 13, 4025-4031

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SEM images of the as-synthesized ZnS nanowire bundles

Researchers from China have recently described the controlled synthesis of ZnS nanowire bundles and nanorod arrays though directly etching zinc wafer at mild temperature. Unique yellow photoluminescence emissions of the as-obtained ZnS nanostructures were observed. The as-synthesized ZnS nanorod arrays possess good superhydrophobicity making the nanostructures  excellent candidates for optics and biomimetics.

Read more about these interesting nanostructures at:

Self assembly of shape-controlled ZnS nanostructures with novel yellow light photoluminescence and excellent hydrophobic properties
Weina Jia, Boxiang Jia, Xiang Wu and Fengyu Qu
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE25144B

Shearing, bending or brittle?

C. Malla Reddy and colleagues study polymorphic forms of 6-chloro-2,4-dinitroaniline to demonstrate a direct relationship between mechanical properties, crystal structure and tableting behaviour in this HOT CrystEngComm communication.  Understanding the structure-property relationships ocurring in pharmaceuticals and using this knowledge to eliminate inferior active pharmaceutical ingredient properties could play an important role in reducing formulation and manufacturing costs in the industry.

Why not take a look, they will be free to read for 4 weeks.

Direct correlation among crystal structure, mechanical behaviour and tabletability in a trimorphic molecular compound
Partha Pratim Bag,  Miles Chen,  Changquan Calvin Sun and C. Malla Reddy
CrystEngComm, 2012
DOI: 10.1039/C2CE25100K

CrystEngComm, 2012, 14, 2335-2596

You may also be interested in taking a look at our recent themed issue on Crystal engineering and crystallography in the pharmaceutical industry.

Remember you can keep up to date with all the latest news in crystal engineering by liking us on facebook, following us on twitter or signing up to our e-alert service.

Arrangement of the heterorings

Thiometalates have been increasingly under the spotlight in recent years due to their attractive properties such as tuneable band gaps, photoconductivity and magnetic properties. In this HOT article, Bensch et al. describe a new synthetic strategy which employs a Ni²⁺ complex as a structure-directing molecule to form a novel 3D thioantimonate(III) with a new network topology. The synthetic route should be applicable for the generation of other thiometalates with new networks and topologies.

Read more for FREE for 4 weeks at:

Using a Ni²⁺ complex as a structure-directing molecule: solvothermal synthesis and properties of [Ni(en)(tren)]₄Sb₁₄S₂₅ featuring an unprecedented three-dimensional network architecture
Beatrix Seidlhofer, Christian Näther and Wolfgang Bensch
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE25141H

Also of interest:

Antimonato polyoxovanadates with structure directing transition metal complexes: pseudopolymorphic {Ni(dien)₂}₃[V₁₅Sb₆O₄₂(H₂O)]·nH₂O compounds and {Ni(dien)₂}₄[V₁₆Sb₄O₄₂(H₂O)]
Elena Antonova, Christian Näther and Wolfgang Bensch
Dalton Trans., 2012, 41, 1338-1344
DOI: 10.1039/C1DT11635E, Paper

Remember you can keep up to date with all the latest news in crystal engineering by liking us on facebook, following us on twitter or signing up to our e-alert service.

Lately it seems that nanoputian research hasn’t been particularly hot in the world of organic chemistry, however in crystal engineering the controlled morphological design of nanocrystals has arguably never been hotter. In the fields of biomedicine, optics and electronics the potential application of a variety of nanomaterials has sparked interest around the world, with nanotechnology potentially revolutionising science, technology, engineering and medicine.

A sample of FESEM images of the interesting nanocrystal morphologies created by the research team – check out the paper for more details!

The fundamental properties of any nanomaterial are ultimately determined by particle size and shape, so for every potential application it is crucial that morphology is carefully controlled so the materials possess the desired properties. This Hot Article from Wei Zhong et al. details the team’s investigations into a one-step evaporation process to produce a huge range of nanocrystal morphologies, including nanowires, nanoswords, nanobelts, nanocombs and branched nanorods. To find out how the team achieved this, download their article now, which is free to access for 4 weeks!

Design, growth, and characterization of morphology-tunable Cd_xZn_1−xS nanostructures generated by a one-step thermal evaporation process
Zai-Xing Yang, Peng Zhang, Wei Zhong, Yu Deng, Chak-Tong Au and You-Wei Du

Interested in nanocrystals? You can also download these great articles which are also free to access!

Highly active Zn_xCd_1−xS photocatalysts containing earth abundant elements only for H2 production from water under visible light
Yabo Wang ,  Jianchun Wu ,  Jianwei Zheng and Rong Xu
Catal. Sci. Technol., 2011,1, 940-947
DOI: 10.1039/C1CY00143D

Nanostructured Titania: the current and future promise of Titania nanotubes
Kevin C. Schwartzenberg and Kimberly A. Gray
Catal. Sci. Technol., 2012, Advance Article
DOI: 10.1039/C2CY00538G

Efficient conversion of solar energy to electricity is a dream we all share, in the natural world sunlight is the basis for nearly all life (excluding those deep see hydrothermal vents and chemo-autotrophic bacteria based communities!). If we could mimic this in our modern world, powering transport, industry and domestic environments with an environmentally friendly, abundant and free power source, we would surely be better off………….. but what’s the best way to do it?

SnO2 hollow nanospheres in DSSC's can give light-to-electricity conversion efficiencies of up to 6.02%

Dye sensitized solar cells (DSSC’s) have been an attractive prospect for some time now, they are relatively cheap and their light harvesting efficiency is dependent on dye absorption and charge separation. By designing hollow SnO₂ nanospheres enclosed with single crystalline nanoparticles, Jinghong Li and Lin Guo et al. have achieved a light-to-electricity conversion efficiency of 6.02%, which is among the highest in non-TiO₂ semiconductor oxides.

The nanostructure design means there is a very high surface area, allowing absorption of a great number of dye molecules, while the single crystalline structure has efficient charge separation properties. This design is proving to be a great candidate for future DSSC technologies…

SnO₂ hollow nanospheres enclosed by single crystalline nanoparticles for highly efficient dye-sensitized solar cells
Hua Wang, Bo Li, Jian Gao, Ming Tang, Hongbin Feng, Jinghong Li and Lin Guo

New synthesis route for metal fluorosulphates

Cathodes made from olivine-type LiFePO₄ are currently being investigated for use in batteries thanks to having properties such as high structural stability, low production costs and high theoretical capacities – but they are currently restricted by being unable to provide sufficient voltage.  A possible way to increase the voltage in such a system could be the isostructural replacement of (PO₄)^3- with (SO₄)^2- as well as the introduction of fluorine.

In their CrystEngComm Communication, Yongchun Zhu, Yitai Qian and colleagues have prepared the compound NaFeSO₄F in a single, short step (previous methods have taken more than 40 hours) using a benzene-water azeotrope, which is a mixture of liquids that boils at a constant temperature, maintaining the ratio of constituents. 
Could this method be adapted to synthesise other fluorosulphates in one step, such as LiZnSO₄F or NaZNSO₄F, for use as cathode materials?

Read the Communication to find out more – it’s currently free.

A novel benzene–water azeotrope route to new Na-based metal fluorosulphates NaFeSO₄F and NaFeSO₄F·2H₂O in one minute
Zhengqiu Yuan, Denghu Wei, Yan Wang, Yongchun Zhu, Yitai Qian and Kaibing Tang
CrystEngComm, 2012
DOI: 10.1039/C2CE25155H

Remember you can keep up to date with all the latest news in crystal engineering by liking us on facebook, following us on twitter or signing up to our e-alert service.

Carbaborane C-H groups are acidic and so are able to form hydrogen bonding interactions as donors. This can be exploited in the use of carbaboranes as coordinating anions that can be involved in agostic interactions with diverse metal centres. Agostic and electrostatic interactions for Ag···H-B are very rare.

In this advance article, Luís Cunha-Silva and Michaele Hardie report the synthesis and structural characterisation of two silver alkanedinitrile networks with cobalt carbaborane anions that have an exciting mix of short-range Ag···H interactions and geometries.

The complexes exhibit Ag centres that are purely coordinated by Ag···H-B interactions, which are highly uncommon coordination motifs. Both Ag···(H-B)₄ and Ag···(H-B)₆ centres were identified, and the cobalt carbaborane anions behaved as ligands through a mix of these agostic and electrostatic interactions.

This Hot Article is free to access for 4 weeks. You can keep up to date with the latest news in crystal engineering by liking us on facebook, following us on twitter or signing up to our e-alert service!

Linear halogen bond assembly

Lee Brammer and colleagues report crystal structures of halogen-bonded adducts between diiodoacetylene and nitrogen/oxygen acceptor groups showing the suitability of diiodoacetylene as a ditopic connector. 

The strength in the halogen bond is due to the electron-withdrawing effect from the sp-hybridised carbon atom in diiodoacetyle.  Being able to form such strong intermolecular interactions via such a small linear molecule with two conformationally constrained faces makes diiodoacetylene a useful building block in crystal engineering and supramolecular chemistry.

Read the paper for free…

Diiodoacetylene: compact, strong ditopic halogen bond donor
Catherine Perkins,  Stefano Libri,  Harry Adams and Lee Brammer
CrystEngComm, 2012
DOI: 10.1039/C2CE00029F

Here is a selection of other recent work from Lee Brammer and colleagues…

Different structural destinations: comparing reactions of [CuBr2(3-Brpy)2] crystals with HBr and HCl gas
Guillermo Mínguez Espallargas, Alastair J. Florence, Jacco van de Streek and Lee Brammer
CrystEngComm, 2011, 13, 4400-4404
DOI: 10.1039/C1CE05222E
From themed issue Dynamic behaviour and reactivity in crystalline solids

Synthesis and polymorphism of (4-ClpyH)2[CuCl4]: solid–gas and solid–solid reactions
Iñigo J. Vitorica-Yrezabal, Rachel A. Sullivan, Stephen L. Purver, Caroline Curfs, Chiu C. Tang and Lee Brammer
CrystEngComm, 2011, 13, 3189-3196
DOI: 10.1039/C0CE00628A
From themed issue Reactions in molecular solids and host–guest systems

Effects of halogen bonding in ferromagnetic chains based on Co(II) coordination polymers
Juan M. Clemente-Juan, Eugenio Coronado, Guillermo Mínguez Espallargas, Harry Adams and Lee Brammer
CrystEngComm, 2010, 12, 2339-2342
DOI: 10.1039/C003078C
From themed issue New Talent