Tag Archives: Amy A. Sarjeant

Capturing neon in an organic environment

Neon observed experimentally within the pores of NiMOF-74 at 100 K and 100 bar of neon gas pressure Courtesy: Cambridge Crystallographic Data Centre (CCDC)

Neon observed experimentally within the pores of NiMOF-74 at 100 K and 100 bar of neon gas pressure Courtesy: Cambridge Crystallographic Data Centre (CCDC)

An Aug. 10, 2016 news item on Nanowerk announces the breakthrough (Note: A link has been removed),

In a new study, researchers from the Cambridge Crystallographic Data Centre (CCDC) and the U.S. Department of Energy’s (DOE’s) Argonne National Laboratory have teamed up to capture neon within a porous crystalline framework. Neon is well known for being the most unreactive element and is a key component in semiconductor manufacturing, but neon has never been studied within an organic or metal-organic framework until now.

The results (Chemical Communications, “Capturing neon – the first experimental structure of neon trapped within a metal–organic environment”), which include the critical studies carried out at the Advanced Photon Source (APS), a DOE Office of Science user facility at Argonne, also point the way towards a more economical and greener industrial process for neon production.

An Aug. 10, 2016 Cambridge Crystallographic Data Centre (CCDC) press release, which originated the news item, explains more about neon and about the new process,

Neon is an element that is well-known to the general public due to its iconic use in neon signs, especially in city centres in the United States from the 1920s to the 1960s. In recent years, the industrial use of neon has become dominated by use in excimer lasers to produce semiconductors. Despite being the fifth most abundant element in the atmosphere, the cost of pure neon gas has risen significantly over the years, increasing the demand for better ways to separate and isolate the gas.

During 2015, CCDC scientists presented a talk at the annual American Crystallographic Association (ACA) meeting on the array of elements that have been studied within an organic or metal-organic environment, challenging the crystallographic community to find the next and possibly last element to be added to the Cambridge Structural Database (CSD). A chance encounter at that meeting with Andrey Yakovenko, a beamline scientist at the Advanced Photon Source, resulted in a collaborative project to capture neon – the 95th element to be observed in the CSD.

Neon’s low reactivity, along with the weak scattering of X-rays due to its relatively low number of electrons, means that conclusive experimental observation of neon captured within a crystalline framework is very challenging. In situ high pressure gas flow experiments performed at X-Ray Science Division beamline 17-BM at the APS using the X-ray powder diffraction technique at low temperatures managed to elucidate the structure of two different metal-organic frameworks with neon gas captured within the materials.

“This is a really exciting moment representing the latest new element to be added to the CSD and quite possibly the last given the experimental and safety challenges associated with the other elements yet to be studied” said Peter Wood, Senior Research Scientist at CCDC and lead author on the paper published in Chemical Communications. “More importantly, the structures reported here show the first observation of a genuine interaction between neon and a transition metal, suggesting the potential for future design of selective neon capture frameworks”.

The structure of neon captured within the framework known as NiMOF-74, a porous framework built from nickel metal centres and organic linkers, shows clear nickel to neon interactions forming at low temperatures significantly shorter than would be expected from a typical weak contact.

Andrey Yakovenko said “These fascinating results show the great capabilities of the scientific program at 17-BM and the Advanced Photon Source. Previously we have been doing experiments at our beamline using other much heavier, and therefore easily detectable, noble gases such as xenon and krypton. However, after meeting co-authors Pete, Colin, Amy and Suzanna at the ACA meeting, we decided to perform these much more complicated experiments using the very light and inert gas – neon. In fact, only by using a combination of in situ X-ray powder diffraction measurements, low temperature and high pressure have we been able to conclusively identify the neon atom positions beyond reasonable doubt”.

Summarising the findings, Chris Cahill, Past President of the ACA and Professor of Chemistry, George Washington University said “This is a really elegant piece of in situ crystallography research and it is particularly pleasing to see the collaboration coming about through discussions at an annual ACA meeting”.

The paper describing this study is published in the journal Chemical Communications, http://dx.doi.org/10.1039/C6CC04808K. All of the crystal structures reported in the paper are available from the CCDC website: http://www.ccdc.cam.ac.uk/structures?doi=10.1039/C6CC04808K.

Here’s another link to the paper but this time with a citation for the paper,

Capturing neon – the first experimental structure of neon trapped within a metal–organic environment by
Peter A. Wood, Amy A. Sarjeant, Andrey A. Yakovenko, Suzanna C. Ward, and Colin R. Groom. Chem. Commun., 2016,52, 10048-10051 DOI: 10.1039/C6CC04808K First published online 19 Jul 2016

The paper is open access but you need a free Royal Society of Chemistry publishing personal account to access it.

Love, hate, and the whole damn thing affect batteries, semiconductors, and electronic memory

A Jan. 24, 2013 news item on ScienceDaily features love triumphing over hate where tetracationic rings are concerned,

Northwestern University graduate student Jonathan Barnes had a hunch for creating an exotic new chemical compound, and his idea that the force of love is stronger than hate proved correct. He and his colleagues are the first to permanently interlock two identical tetracationic rings that normally are repelled by each other. Many experts had said it couldn’t be done.

On the surface, the rings hate each other because each carries four positive charges (making them tetracationic). But Barnes discovered by introducing radicals (unpaired electrons) onto the scene, the researchers could create a love-hate relationship in which love triumphs.

The Jan. 24, 2013 Northwestern University news release by Megan Fellman, which originated the news item, probes into the nature of the problem and its solution (Note: A link has been removed),

Unpaired electrons want to pair up and be stable, and it turns out the attraction of one ring’s single electrons to the other ring’s single electrons is stronger than the repelling forces.

The process links the rings not by a chemical bond but by a mechanical bond, which, once in place, cannot easily be torn asunder.

The study detailing this new class of stable organic radicals will be published Jan. 25 [2013] by the journal Science.

“It’s not that people have tried and failed to put these two rings together — they just didn’t think it was possible,” said Sir Fraser Stoddart, a senior author of the paper. “Now this molecule has been made. I cannot overemphasize Jonathan’s achievement — it is really outside the box. Now we are excited to see where this new chemistry leads us.”

The rings repel each other like the positive poles of two magnets. Barnes saw an opportunity where he thought he could tweak the chemistry by using radicals to overcome the hate between the two rings.

“We made these rings communicate and love each other under certain conditions, and once they were mechanically interlocked, the bond could not be broken,” Barnes said.

Barnes’ first strategy — adding electrons to temporarily reduce the charge and bring the two rings together — worked the first time he tried it. He, Stoddart and their colleagues started with a full ring and a half ring that they then closed up around the first ring (using some simple chemistry), creating the mechanical bond.

When the compound is oxidized and electrons lost, the strong positive forces come roaring back — “It’s hate on all the time,” Barnes said — but then it is too late for the rings to be parted. “That’s the beauty of this system,” he added.

Most organic radicals possess short lifetimes, but this unusual radical compound is stable in air and water. The compound tucks the electrons away inside the structure so they can’t react with anything in the environment. The tight mechanical bond endures despite the unfavorable electrostatic interactions.

The two interlocked rings house an immense amount of charge in a mere cubic nanometer of space. The compound, a homo[2]catenane, can adopt one of six oxidation states and can accept up to eight electrons in total.

“Anything that accepts this many electrons has possibilities for batteries,” Barnes said.

“Applications beckon,” Stoddart agreed. “Now we need to spend more time with materials scientists and people who make devices to see how this amazing compound can be used.”

For anyone interested in the details of the work, here’s a citation and link to the paper published in Science,

A Radically Configurable Six-State Compound by Jonathan C. Barnes, Albert C. Fahrenbach, Dennis Cao, Scott M. Dyar, Marco Frasconi, Marc A. Giesener, Diego Benítez, Ekaterina Tkatchouk, Oleksandr Chernyashevskyy, Weon Ho Shin, Hao Li, Srinivasan Sampath, Charlotte L. Stern, Amy A. Sarjeant, Karel J. Hartlieb, Zhichang Liu, Raanan Carmieli, Youssry Y. Botros, Jang Wook Choi, Alexandra M. Z. Slawin, John B. Ketterson, Michael R. Wasielewski, William A. Goddard III, J. Fraser Stoddart. Science 25 January 2013: Vol. 339 no. 6118 pp. 429-433 DOI: 10.1126/science.1228429

This is paper is behind a paywall.