Those reactions on a gold base pioneering a "new chemistry"

EMPA and the Max Planck Institute had molecules standing next to each other combine (and "photograph") in ultra-high vacuum

New chemistry: working pattern of 3+3-cyclodiffusion discovered in the "Nanotech@Surfaces" laboratory of EMPA in Switzerland
An artistic rendering of the 3+3-cyclodiffusion discovered in the “Nanotech@Surfaces” laboratory of EMPA in Switzerland
(Photo: EMPA)

Chemical syntheses in liquids and gases take place in three-dimensional space. Random collisions between molecules must lead to something new in an extremely short time.
But there is another method: on a gold surface, under conditions of high vacuum, it is possible to combine molecules stationary next to each other, including those that would never want to react spontaneously with each other in a liquid.
Researchers from EMPA and the Max Planck Institute have now discovered such a reaction. And above all, experts can "photograph" and observe each stage of the reaction.

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New Chemistry: An Artist's Rendering of 3+3-Cyclodiffusion Discovered in EMPA's "Nanotech@Surfaces" Lab in Switzerland
An artistic rendering of the 3+3-cyclodiffusion discovered in the “Nanotech@Surfaces” laboratory of EMPA in Switzerland
(Photo: EMPA)

The benzene rings of graphene and graphite, but also of indigo for jeans and aspirin

In chemistry there are particularly stable structures, such as the so-called "benzene ring", composed of six interconnected carbon atoms.
These rings form the structural basis of graphite and graphene, but are also present in many dyes, such as indigo for jeans, and many drugs, such as aspirin.
When chemists wanted to construct such rings in a targeted way, they used so-called coupling reactions, which usually bear the name of their inventors: for example, the Diels-Alder reaction, the Ullmann reaction, the Bergman cyclization or the Suzuki coupling.
Now there's another one that doesn't have a name yet.
It was discovered by a team from the Swiss Federal Laboratory for Materials Testing and Research together with the Max Planck Institute for Polymer Research in Mainz, Germany.

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New Chemistry: An Artist's Rendering of 3+3-Cyclodiffusion Discovered in EMPA's "Nanotech@Surfaces" Lab in Switzerland
An artistic rendering of the 3+3-cyclodiffusion discovered in the “Nanotech@Surfaces” laboratory of EMPA in Switzerland
(Photo: EMPA)

Diisopropyl-p-terphenyl as a "resting phase" starting material on a gold surface

The EMPA researchers omitted the liquids in their chemical synthesis and instead attached the starting materials to a gold surface in an ultra-high vacuum.
The starting material (diisopropyl-p-terphenyl) can be observed resting quietly in the cooled tunneling microscope before the researchers turn up the heat.

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New chemistry: working pattern of 3+3-cyclodiffusion discovered in the "Nanotech@Surfaces" laboratory of EMPA in Switzerland
Functional scheme of the 3+3-cyclodiffusion discovered in the “Nanotech@Surfaces” laboratory of EMPA in Switzerland
(Photo: EMPA)

At 200 degrees Celsius, the surprising reaction that would never occur in liquids takes place

At room temperature nothing happens yet, but at about 200 degrees Celsius an amazing reaction takes place, which would never occur in liquids.
The two isopropyl groups, which are normally completely chemically inactive, combine to form a benzene ring.
The reason: Due to the strong "adhesion" on the gold surface, a hydrogen atom is first loosened and then released from the molecule.
This creates carbon radicals that are waiting for new partners. And on the surface of gold there are many partners…
At 200 degrees Celsius, the molecules vibrate and perform rapid pirouettes: there is a lot of movement on the… golden “dance floor”.
Thus, what belongs to one or the other quickly aggregates.

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New Chemistry: An Artist's Rendering of 3+3-Cyclodiffusion Discovered in EMPA's "Nanotech@Surfaces" Lab in Switzerland
An artistic rendering of the 3+3-cyclodiffusion discovered in the “Nanotech@Surfaces” laboratory of EMPA in Switzerland
(Photo: EMPA)

How to see and “snap” various molecules just before they “marry” each other

Gold surface encounters have two advantages.
First, there is no need for coercion: the reaction occurs without mediating boric acids or volatile halogen atoms.
This is a coupling involving only saturated hydrocarbons.
The starting materials are cheap and easy to obtain, and there are no toxic byproducts.
The second advantage is that researchers can observe each step of the reaction: another opportunity that is not possible at all with classical, "liquid" chemistry.
The EMPA team simply increases the heating of the gold surface gradually.
At 180 degrees Celsius, the molecules have linked only one arm with their neighbors, while the second still protrudes freely onto the dance floor.
If you now cool the gold surface inside a tunneling microscope, you can see and 'photograph' the molecules just before they 'marry'.
This is exactly what the researchers did.
In this way, the reaction mechanism can be followed in the form of "snapshots".

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New Chemistry: An Artist's Rendering of 3+3-Cyclodiffusion Discovered in EMPA's "Nanotech@Surfaces" Lab in Switzerland
An artistic rendering of the 3+3-cyclodiffusion discovered in the “Nanotech@Surfaces” laboratory of EMPA in Switzerland
(Photo: EMPA)

Reactions engineered under a tunneling microscope and then transferred to liquid or gaseous chemistry?

The Swiss researchers and their German colleagues expect two types of effects to emerge from the current work.
First, the "snapshot method" might also be suitable for elucidating completely different reaction mechanisms.
At the Federal Materials Testing and Research Laboratory, instruments are being developed that use ultrashort laser pulses in a tunneling microscope to elucidate such chemical reactions step by step.
This could provide further insights into chemical reactions and soon shake up many old theories.
However, the results of 'dry' research could also be useful for further developing 'liquid' chemistry.
So far, most of the reactions documented in the literature come from classical liquid chemistry, and scanning probe researchers have been able to recreate these experiments.
In the future, some reactions could be engineered under a tunneling microscope and later transferred to liquid or gaseous chemistry. In Switzerland discovered a material that "remembers" like the brain

New Chemistry: An artist's rendering of 3+3-cyclodiffusion discovered in the lab
An artist's rendering of the 3+3-cyclodiffusion discovered in EMPA's "Nanotech@Surfaces" laboratory in Switzerland (Photo: EMPA)