Sciencemadness Discussion Board - Some C60 Chemistry

Some C60 Chemistry

VSEPR_VOID - 15-11-2018 at 15:32

As part of a project for school I am making aromatic amine C60 fullerene adducts. Here is some pictures of them.

Does anyone else have an interest in C60 chemistry? C60 has recently dropped in price, is very easy to make with a vacuum chamber and arc welder, has colorful derivatives, and is a new frontier.

Ubya - 15-11-2018 at 15:53

i was planning in making some C60 as i have a vacuum chamber (and i will build the arc welder). it's interesting the fact that is a carbon allotrope solubile in toluene and many other solvents

fusso - 15-11-2018 at 16:02

Remember to see if it can react with piranha soln!

VSEPR_VOID - 15-11-2018 at 16:29

Quote: Originally posted by Ubya

i was planning in making some C60 as i have a vacuum chamber (and i will build the arc welder). it's interesting the fact that is a carbon allotrope solubile in toluene and many other solvents

You cand find many papers on it that go into detail. All it requires in graphite rods, vacuum, and some He to use an an inert gas.

Further more, if you have a soxhlet extraction and purification is easy using chloroform or toluene

Imagine if we had a C60 sticky! If we had a member making C60 (you can make easily a gram a day) then we could all start C60 related projects.

[Edited on 16-11-2018 by VSEPR_VOID]

12thealchemist - 16-11-2018 at 01:01

I have several kilograms of soot which I plan to extract at some point in the distant future with a Soxhlet extractor with several solvents, gradually decreasing in polarity, to extract the various soluble components, including fullerenes. I'm aware that these are likely present at less than 1%, but 1 kg @ 0.1% = 1 g, which is extremely valuable.

VSEPR_VOID - 16-11-2018 at 07:12

Quote: Originally posted by 12thealchemist

I have several kilograms of soot which I plan to extract at some point in the distant future with a Soxhlet extractor with several solvents, gradually decreasing in polarity, to extract the various soluble components, including fullerenes. I'm aware that these are likely present at less than 1%, but 1 kg @ 0.1% = 1 g, which is extremely valuable.

How was the soot generated? If it was generated by regular fullerene methods than it should be more than 10% C60. If it was made by burning wood in air, or something similar, than the C60 should be in very small trace amounts (a lot less than 1%). In addition, you would have to consider the organic residues that saturate the wood.

12thealchemist - 16-11-2018 at 07:28

Unfortunately, I don't know the origin of the soot. It was sold originally for gardening purposes, so it could be coal and/or wood soot. Either way, even if it doesn't have fullerenes, it will probably contain something interesting.

Mr. Rogers - 16-11-2018 at 07:53

Does anyone know what the deal is with C60 Olive Oil? What is this about?

https://www.amazon.com/s/ref=nb_sb_noss?url=search-alias%3Da...

[Edited on 16-11-2018 by Mr. Rogers]

VSEPR_VOID - 16-11-2018 at 07:59

There was a paper a long time ago that provided evidence that C60 had some medicinal value scavenging radicals; health nuts jumped on it for its mystical powers.

Ubya - 16-11-2018 at 08:56

Quote: Originally posted by VSEPR_VOID

if you have a soxhlet extraction and purification is easy using chloroform or toluene

[Edited on 16-11-2018 by VSEPR_VOID]

i did not think of using a soxhler extractor, but this is a good idea, one more reason to buy it

VSEPR_VOID - 16-11-2018 at 14:23

Yeah, you can even pack the soxhlet with activated carbon or alumina and purify the extract via chromatography. There are lots of papers out there. I really want to make a C60 reactor one day.

VSEPR_VOID - 18-11-2018 at 08:08

This should be C60(C6H5CH2CH2CH2NH2)12
Just got done purifying it with IPA washings

It forms deep red solutions in hot IPA, chloroform, and phenylpropylamine.

Tsjerk - 18-11-2018 at 08:52

How did you prepare it?

VSEPR_VOID - 18-11-2018 at 09:03

I hopefully will have the paper out within the year. I am working with a real research lab. It was prepared using a very simple one-pot reaction between the corresponding aromatic and C60 with a aluminium halide catalyst.

Purification has been the hardest part. Soon I will be using mass spectroscopy to confirm my product.

Texium - 18-11-2018 at 09:07

Well this thread isn't exactly "C60 Chemistry" then, is it? It's more like, "a couple pictures of a purported C60 derived compound that hasn't been verified and some vague allusions to how it was made."

fusso - 18-11-2018 at 09:32

Quote: Originally posted by VSEPR_VOID

This should be C60(C6H5CH2CH2CH2NH2)12

Did you mean: "C6H4"?

Tsjerk - 18-11-2018 at 09:49

Quote: Originally posted by VSEPR_VOID

I hopefully will have the paper out within the year. I am working with a real research lab. It was prepared using a very simple one-pot reaction between the corresponding aromatic and C60 with a aluminium halide catalyst.

Purification has been the hardest part. Soon I will be using mass spectroscopy to confirm my product.

It won't hurt anyone explaining what you did.

VSEPR_VOID - 18-11-2018 at 10:33

Quote: Originally posted by Tsjerk

Quote: Originally posted by VSEPR_VOID

It won't hurt anyone explaining what you did.

Okay, sorry for the confusion

10 mL of an aromatic amine (aniline or phenylpropylamine for example) was placed into a glass tube with 50 mg of anhydrous aluminium chloride and 50 mg of C60.

The tube was sealed then agitated for 2 hours to mix the reaction components well. The tube was left to react for 3 days.

After 3 days the color was a very dark red.

Washing with water, to remove the catalyst, and work up and evaporation with chloroform left a thick residue containing the amine and C60 adduct.

This was then purified via recrystlization with hot 99.5% ISPA (3 mL for ever 0.5 g of residue). Upon cooling the ISPA with ice, the precipitate was collected then washed with fresh ice cold ISPA.

Attached is a paper on purifying C60 soot with a soxhlet extractor.

Attachment: A simple Soxhlet chromatographic method for the isolation of pure fullerenes C60 and C70.pdf (998kB)
This file has been downloaded 434 times

Quote: Originally posted by fusso

Quote: Originally posted by VSEPR_VOID

This should be C60(C6H5CH2CH2CH2NH2)12

Did you mean: "C6H4"?

No, here is the molecule https://www.sigmaaldrich.com/catalog/product/aldrich/p32406?...

[Edited on 18-11-2018 by VSEPR_VOID]

DrP - 20-11-2018 at 06:50

Quote: Originally posted by VSEPR_VOID

Let us know how that goes. :-) The mass spec and the paper. :-) Good luck. :-)

VSEPR_VOID - 20-11-2018 at 07:58

I will. It will find its way into the prepublications.

I also want to try out the same reaction but with aromatic alcohols and carboxylic acid in place of the amines.

DrP - 20-11-2018 at 08:12

I am afraid I do very little chemistry like this - C60 has always fascinated me though since I first heard about it in the 1980s and then learnt about some of it's chemistry at uni in the 90s. I expect we know so much more about it now than we did then.

If I remember rightly (which I probably don't) - does it react with other atoms as if it was an atom with valence II? I seem to remember that it can accept or donate 2 electrons... something like that - this was over 20 years ago so I am probably not remembering it correctly or we have moved on from then and learnt more. Please excuse my total lack of knowledge about it - I just find the structure interesting as a new allotrope of carbon.

VSEPR_VOID - 20-11-2018 at 09:08

C60 behaves as a super electron deficient polyalkene. It undergoes a variety of reactions to form many adducts. For example, C60 is very reactive with grignard reagents.

Most reactions with C60 are driven forward because of strain relief from the double bonds becoming single bonds. This however, can be counter acted by the eclipsing of the added groups causing more steric strain. An example of this is polyhydrogenated C60. C60H60 is not stable and does not form, but C60H36 is the most stable hydrogenated derivative. It has just enough 1,2 additions (which reduce the strain caused by double bonds) to counteract the strain from eclipsed hydrogens.

C60, in addition to having a very reactive exterior, has endohedral chemistry as well. Because of steric hindrance, the inside of C60 acts as a sort of chemical Feriday cage. As a result, exotic or reactive species (such as nitrogen radicals) can be trapped inside and studied.

Right now a lot of research is being conducted on opening holes in the C60 cage, inserting an element or molecule inside, then closing that hole.

fusso - 20-11-2018 at 10:33

Quote: Originally posted by VSEPR_VOID

Quote: Originally posted by fusso

Quote: Originally posted by VSEPR_VOID

This should be C60(C6H5CH2CH2CH2NH2)12

Did you mean: "C6H4"?

No, here is the molecule https://www.sigmaaldrich.com/catalog/product/aldrich/p32406?...

[Edited on 18-11-2018 by VSEPR_VOID]

Yes I know I mean the R-C6H5 should lose 1 H when it react with C60 in a friedel craft to form C60-C6H4-R isnt it?

walruslover69 - 20-11-2018 at 10:37

How do you control the number of adducts that attach to the C60?

Tsjerk - 20-11-2018 at 11:08

What is the solubility of C60 in the solvent anyone would typically use for a soxhlet?

walruslover69 - 20-11-2018 at 11:09

wikipedia has a great chart

in g/L
1-chloronaphthalene 51
1-methylnaphthalene 33
tetrahydronaphthalene 16
carbon disulfide 8
1,2,3-tribromopropane 8
xylene 5
bromoform 5
cumene 4
toluene 3
benzene 1.5
carbon tetrachloride 0.447
chloroform 0.25
n-hexane 0.046
cyclohexane 0.035
tetrahydrofuran 0.006

Tsjerk - 20-11-2018 at 11:47

Ok, then I get the soxhlet method over just soaking and filtering.

walruslover69 - 20-11-2018 at 13:04

The chromatography step seems very important as to separate other fullerenes and side products.

VSEPR_VOID - 20-11-2018 at 16:50

Quote: Originally posted by fusso

Yes I know I mean the R-C6H5 should lose 1 H when it react with C60 in a friedel craft to form C60-C6H4-R isnt it?

The extra hydrogen also bonds to the C60 cage giving C60Hn(C6H4-R)n where n has been reported to be primarily 12.

I may have had a typo there or something got lost in translation, my bad.

Quote: Originally posted by walruslover69

How do you control the number of adducts that attach to the C60?

For the reaction I am doing you can not, or it has not been discovered how.

12 just is the most common number of additions, with 16 being reported in very small amounts.

Quote: Originally posted by Tsjerk

Ok, then I get the soxhlet method over just soaking and filtering.

Yes, if you use a solvent like toluene, chloroform, or benzene it will be very easy. In addition you can use the same equipment and reagents (in addition to some charcoal and alumina) to purify your fullerenes so you only get C60, and not C60 and C70.

[Edited on 21-11-2018 by VSEPR_VOID]

DrP - 21-11-2018 at 01:01

Quote: Originally posted by VSEPR_VOID

C60 behaves as a super electron deficient polyalkene. It undergoes a variety of reactions to form many adducts. For example, C60 is very reactive with grignard reagents.

Most reactions with C60 are driven forward because of strain relief from the double bonds becoming single bonds. This however, can be counter acted by the eclipsing of the added groups causing more steric strain. An example of this is polyhydrogenated C60. C60H60 is not stable and does not form, but C60H36 is the most stable hydrogenated derivative. It has just enough 1,2 additions (which reduce the strain caused by double bonds) to counteract the strain from eclipsed hydrogens.

C60, in addition to having a very reactive exterior, has endohedral chemistry as well. Because of steric hindrance, the inside of C60 acts as a sort of chemical Feriday cage. As a result, exotic or reactive species (such as nitrogen radicals) can be trapped inside and studied.

Right now a lot of research is being conducted on opening holes in the C60 cage, inserting an element or molecule inside, then closing that hole.

Awesome - thanks for that info. I think the chemistry of it has progressed since I first heard about it. There was a lot of hype about how amazing it would be.... I guess nano tubes get more study due to ease of loading them up and getting stuff out compared to trying to put stuff into a bucky ball and get it out again. There seems to be more hype for nano tubes and grapheme over bucky balls now. I like the radical trap idea... no idea how you'd get something inside it though.

VSEPR_VOID - 21-11-2018 at 13:22

Nanotubes and graphene are definitely cool, but nanotubes are difficult to purify and both nanotubes and graphene are hard to produce at any meaningful size.

Fullerenes on the other hand are easy to make and purify. I think that we as amateurs could really to some neat things with them.

One aspect that should interest amateurs is that many fullerene derrivatives are both easy to make and have never been made before. Take for example my amine adduct, first in the world.

mayko - 9-2-2019 at 09:50

An interesting fullerene paper I ran across:

Zhu, S.-E., Li, F., & Wang, G.-W. (2013). Mechanochemistry of fullerenes and related materials. Chemical Society Reviews, 42(18), 7535. http://doi.org/10.1039/c3cs35494f

Quote:

The low or lack of solubility of fullerenes, carbon nanotubes and graphene/graphite in organic solvents and water severely hampers the study of their chemical functionalizations and practical applications. Covalent and noncovalent functionalizations of fullerenes and related materials via mechanochemistry seem appealing to tackle these problems. In this review article, we provide a comprehensive coverage on the mechanochemical reactions of fullerenes, carbon nanotubes and graphite, including dimerizations and trimerizations, nucleophilic additions, 1,3-dipolar cycloadditions, Diels–Alder reactions, [2 + 1] cycloadditions of carbenes and nitrenes, radical additions, oxidations, etc. It is intriguing to find that some reactions of fullerenes can only proceed under solvent-free conditions or undergo different reaction pathways from those of the liquid-phase counterparts to generate completely different products. We also present the application of the mechanical milling technique to complex formation, nanocomposite formation and enhanced hydrogen storage of carbon-related materials.

Attachment: Mechanochemistry of fullerenes and related materials.pdf (4.3MB)
This file has been downloaded 448 times