Forum for Science, Industry and Business

Sponsored by:     3M 
Search our Site:


Molecular Hinges Open Pathways

Exchange of bismuth atoms for chloride ions with retention of structure

Modern technology makes extensive use of ion exchangers. For example, they are commonly used to decalcify water by binding calcium ions and releasing sodium ions in return. Good exchangers tend to be materials with high surface areas, such as resins, zeolites, or clays. German scientists have now demonstrated that the compact, crystalline structures of intermetallic compounds, in which the diffusion pathways for efficient materials transport are actually absent, can also exchange ions. In the journal Angewandte Chemie, they report the full replacement of the chloride ions in Bi12Rh3Cl2 crystals by bismuth atoms.

The team working with Michael Ruck at the Technical University of Dresden noticed this unexpected phenomenon while researching bismuth subhalides. Subhalides are compounds that have fewer halogen ions than pure ionic metal halides. This results in regions that contain direct bonds between metal atoms. Subhalides with bismuth and rhodium are known to have intermetallic substructures that range from clusters to three-dimensional networks. Bi12Rh3Cl2  contains intermetallic networks consisting of edge-sharing [RhBi8] cubes and antiprisms.

The researchers planned to “pull” the halogen atoms out without destroying the intermetallic regions under gentle conditions using an n-butyllithium solution. The chloride ions were extracted just as the scientists hoped, even though they seemed to be tightly enclosed by the narrow channels of the intermetallic network. Even more surprisingly, the resulting voids in the crystal structure were filled by bismuth atoms. The bismuth atoms came from barely noticeable chemical decomposition of the surface of the crystal.

The resulting product is Bi12Rh3Bi2, a metastable superconductor with a structure identical to that of the subchloride. During the reaction, the morphology of the crystal remains unchanged. “The transformation must be based on efficient transport of chloride ions out and bismuth ions into the network,” says Ruck. Crystallographic studies revealed a small change in the torsion angle of the [RhBi8] antiprisms. “The antiprisms act as hinges in the network,” explains Ruck. “Transient changes in the angle allow wide diffusion pathways to open up parallel to all of the intermetallic strands. Since the diffusion paths intersect, the transport system is three-dimensional.”

Although the intermetallic network only changes very slightly, the electronic properties are significantly different: the subchloride only demonstrates metallic conductivity along special directions that are insulated by nonconducting parts of the structure. In the intermetallic compound, in contrast, the conducting strands are metallically connected through the additional bismuth atoms. They are thus electrically connected, resulting in a three-dimensional metal.

About the Author

Professor Dr. Michael Ruck conducts research and teaches chemistry and food chemistry at the Technical University of Dresden. He works in the area of solid-state chemistry and is particularly interested in metallic compounds and low-temperature synthesis of materials. He is also a Fellow of the Max Planck Institute of the Chemical Physics of solids in Dresden.

Author: Michael Ruck, Technische Universität Dresden (Germany),

Title: The Topochemical Pseudomorphosis of a Chloride into a Bismuthide

Angewandte Chemie International Edition, Permalink to the article:

| Angewandte Chemie
Further information:

Further reports about: Molecular bismuth Atoms chloride compounds ions pathways rhodium

More articles from Life Sciences:

nachricht Antibody-Drug Compounds and Immunotherapy to Treat Breast Cancer
26.11.2015 | Universität Basel

nachricht Understanding a missing link in how antidepressants work
25.11.2015 | Max Planck Institute of Psychiatry, München

All articles from Life Sciences >>>

The most recent press releases about innovation >>>

Die letzten 5 Focus-News des innovations-reports im Überblick:

Im Focus: Climate study finds evidence of global shift in the 1980s

Planet Earth experienced a global climate shift in the late 1980s on an unprecedented scale, fuelled by anthropogenic warming and a volcanic eruption, according to new research published this week.

Scientists say that a major step change, or ‘regime shift’, in the Earth’s biophysical systems, from the upper atmosphere to the depths of the ocean and from...

Im Focus: Innovative Photovoltaics – from the Lab to the Façade

Fraunhofer ISE Demonstrates New Cell and Module Technologies on its Outer Building Façade

The Fraunhofer Institute for Solar Energy Systems ISE has installed 70 photovoltaic modules on the outer façade of one of its lab buildings. The modules were...

Im Focus: Lactate for Brain Energy

Nerve cells cover their high energy demand with glucose and lactate. Scientists of the University of Zurich now provide new support for this. They show for the first time in the intact mouse brain evidence for an exchange of lactate between different brain cells. With this study they were able to confirm a 20-year old hypothesis.

In comparison to other organs, the human brain has the highest energy requirements. The supply of energy for nerve cells and the particular role of lactic acid...

Im Focus: Laser process simulation available as app for first time

In laser material processing, the simulation of processes has made great strides over the past few years. Today, the software can predict relatively well what will happen on the workpiece. Unfortunately, it is also highly complex and requires a lot of computing time. Thanks to clever simplification, experts from Fraunhofer ILT are now able to offer the first-ever simulation software that calculates processes in real time and also runs on tablet computers and smartphones. The fast software enables users to do without expensive experiments and to find optimum process parameters even more effectively.

Before now, the reliable simulation of laser processes was a job for experts. Armed with sophisticated software packages and after many hours on computer...

Im Focus: Quantum Simulation: A Better Understanding of Magnetism

Heidelberg physicists use ultracold atoms to imitate the behaviour of electrons in a solid

Researchers at Heidelberg University have devised a new way to study the phenomenon of magnetism. Using ultracold atoms at near absolute zero, they prepared a...

All Focus news of the innovation-report >>>



Event News

Fraunhofer’s Urban Futures Conference: 2 days in the city of the future

25.11.2015 | Event News

Gluten oder nicht Gluten? Überempfindlichkeit auf Weizen kann unterschiedliche Ursachen haben

17.11.2015 | Event News

Art Collection Deutsche Börse zeigt Ausstellung „Traces of Disorder“

21.10.2015 | Event News

Latest News

Antibody-Drug Compounds and Immunotherapy to Treat Breast Cancer

26.11.2015 | Life Sciences

Get to the point with electric cars

26.11.2015 | Power and Electrical Engineering

Climate study finds evidence of global shift in the 1980s

26.11.2015 | Studies and Analyses

More VideoLinks >>>