HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.
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Transcript of HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.
![Page 1: HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.](https://reader036.fdocuments.us/reader036/viewer/2022070415/5697bf791a28abf838c827f0/html5/thumbnails/1.jpg)
HWK Nature, 329, 529 (1987)
Polaroid image of the first molecular model of C28
C28
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Mass Spectrum of Carbon Clusters
Heath, Liu, O’Brien, Curl, Kroto and Smalley unpublished data
C28
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Prediction C28 tetravalent and should be stabilised by addition of four H atoms
HK Nature 1987
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Prediction: because strain released and four C6 aromatic rings remain
HK Nature 1987
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C28 should be a giant tetravalent “Superatom”
H W K Nature, 329, 529 (1987)
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Ti
Properties of C28 in detail starting with Ti@C28
with Paul Dunk and Alan Marshall
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U@C28 1993
U
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800750700650600550500450400350300250
800750700650600550500450400350300250
m/z800750700650600550500450400350300250
U@C44
U@C36
800750700650600550500450400350300250
U@C36
800750700650600550500450400350300250
UO2
U@C28
C27
A
B
C
D
E
NHMFL FSU
Laser vaporization of a UO2-graphite target
laser fired at different points in time along the pulse pressure profile
U@C28 is clearly seen to form before larger U@Cn
species
U@C28
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Exxon Data
Cox et al
JACS 110
1588 (1988)
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C32
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Endohedral Fullerene Comparison Spectra
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Delft Buckyball Wkshp Dynamic Z
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WOW
Moment
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Nori Shinohara - Nagoya
Alan Marshall Dr. FT-ICR-MS
Chris Hendrickson
Nathan Kaiser
Paul Dunk
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Rice Group showed that under intense laser irradiation C60 lost C2 fragments sequentially and at C32 blew up completely into small carbon species and atoms
C60 → C58 → C56 → → → → C32 → C2 C2 C2 Cn
(n small)
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C28 should be special - a tetravalent “Superatom” atom
H W Kroto, Nature, 329, 529 (1987)
Polaroid image of the first molecular model of C28
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Mass spectrum of laser vapourised graphite (Rice 1985)
C28
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Sussex NNC
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Sussex NNC
~sp3
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Four Benzenoid aromatic rings remain
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Exxon Data
Cox et al
JACS 110
1588 (1988)
NB
No C22 possible!
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http://www.orchidpalms.com/polyhedra/acrohedra/nearmiss/jsmn.htm
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Sussex NNC
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The structure proposed for C28 contains four triple fused pentagons units arranged in tetrahedral symmetry.
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Predicted stable and semi-stable Fullerenes
image at: www.answers.com/topic/fullerene
C28 C32 C50 C60 C70
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Predicted stable and semi-stable Fullerenes
image at: www.answers.com/topic/fullerene
C28 C32 C50 C60 C70
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C28 should be tetravalent
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C28 should be tetravalent
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U@C28
U
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Ti@C28
Ti
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Ti@Cn distribution (RED) vs. empty cage distribution (BLUE) for FIG (2). Clearly shows titanium has stabilized C28, and other small fullerenes.
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C28 Sussex NNC
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C28 ”superatom” analogue of sp3 carbon atom Suggests Td C28H4 Nature 329 529 (1987)
C28H4
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at: commons.wikimedia.org/wiki/File:Endohedral_fu...
Endohedral Fullerenes can satisfy “valencies” internally
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m/z388387386385384383382
387386385384383382381
100
90
80
70
60
50
40
30
20
10
0
Titanium Rod – Positive ions
M(C28) + M(Ti) = 336 + 48
= 384
C28TiPredicted
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m/z388387386385384383382
387386385384383382381
100
90
80
70
60
50
40
30
20
10
0
C28TiPredicted
C32
C32C32 C32
ca 50 milliDaltons separation
Titanium Rod – Positive ions
M(C28) + M(Ti) = 336 + 48
= 384
M(C32) = 384
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m/z388387386385384383382
387386385384383382381
100
90
80
70
60
50
40
30
20
10
0
Titanium Rod – Positive ions C28TiPredicted
Minus C32 mass peaks
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FT-ICR-MS relative intensities of Ti@Cn vs n
24 28 32 36 40 44 48 n
100
80
60
40
20
0
Abundance rel units
Ti@C28 Ti@C38
Paul Dunk with Harry Kroto and Alan Marshall
Ti@Cn vs n
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(Td) C28 more stable by 717 kJmol-1 than D2
(Td) Ti@C28 more stable by 270 kJmol-1 than D2
David E. Bean, Patrick W. Fowler, University of Sheffield
C28 (D2) C28 (Td)
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image at: www.answers.com/topic/fullerene
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C28 ”superatom” analogue of sp3 carbon atom Suggests Td C28H4 Nature 329 529 (1987)
C28H4
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at: commons.wikimedia.org/wiki/File:Endohedral_fu...
Endohedral Fullerenes can satisfy “valencies” internally
![Page 48: HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.](https://reader036.fdocuments.us/reader036/viewer/2022070415/5697bf791a28abf838c827f0/html5/thumbnails/48.jpg)
FT-ICR-MS relative intensities of Ti@Cn vs n
24 28 32 36 40 44 48 n
100
80
60
40
20
0
Abundance rel units
Ti@C28 Ti@C38
Paul Dunk with Harry Kroto and Alan Marshall
Ti@Cn vs n
![Page 49: HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.](https://reader036.fdocuments.us/reader036/viewer/2022070415/5697bf791a28abf838c827f0/html5/thumbnails/49.jpg)
(Td) C28 more stable by 717 kJmol-1 than D2
(Td) Ti@C28 more stable by 270 kJmol-1 than D2
David E. Bean, Patrick W. Fowler, University of Sheffield
C28 (D2) C28 (Td)
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For the bare cages, the tetrahedral isomer is more stable by 0.273 a.u. (717 kJmol-1). When a titanium atom is encapsulated, this gap decreases to 0.103 a.u. (270 kJmol-1), but the tetrahedral isomer remains the more stable.
David E. Bean, Patrick W. Fowler, University of Sheffield
C28 (D2) C28 (Td)
![Page 51: HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.](https://reader036.fdocuments.us/reader036/viewer/2022070415/5697bf791a28abf838c827f0/html5/thumbnails/51.jpg)
at: commons.wikimedia.org/wiki/File:Endohedral_fu...
![Page 52: HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.](https://reader036.fdocuments.us/reader036/viewer/2022070415/5697bf791a28abf838c827f0/html5/thumbnails/52.jpg)
image at: people.whitman.edu/~hoffman/
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Abundance of Endohedral Fullerenes Ti@Cn vs n
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24 28 32 36 40 44 48 n
100
80
60
40
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0
Abundance rel units
Ti@C28 Ti@C38
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Some of the more stable members of the fullerene family. (a) C28. (b) C32. (c) C50. (d) C60. (e) C70.
image at: www.answers.com/topic/fullerene
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Abundance of Endohedral Fullerenes Ti@Cn vs n
24 28 32 36 40 44 48 n
100
80
60
40
20
0
Abundance rel units
Ti@C28 Ti@C38
![Page 58: HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.](https://reader036.fdocuments.us/reader036/viewer/2022070415/5697bf791a28abf838c827f0/html5/thumbnails/58.jpg)
![Page 59: HWK Nature, 329, 529 (1987) Polaroid image of the first molecular model of C 28 C 28.](https://reader036.fdocuments.us/reader036/viewer/2022070415/5697bf791a28abf838c827f0/html5/thumbnails/59.jpg)
For the bare cages, the tetrahedral isomer is more stable by 0.273 a.u. (717 kJmol-1). When a titanium atom is encapsulated, this gap decreases to 0.103 a.u. (270 kJmol-1), but the tetrahedral isomer remains the more stable.
David E. Bean, Patrick W. Fowler, University of Sheffield
C28 (D2) C28 (Td)