A
solution of C60 in deuterated chloroform (CDCl3) with
tetramethylsilane (TMS) was prepared. The spectrum revealed no peak for
C60 as was expected since it contains no hydrogens. One peak was
displayed, a reference peak for TMS (see Figure 5).
A
sample of C60 was dispersed in KBr. Peaks at 2384.48
cm-1, 2348.79 cm-1, 1426.96 cm-1, 1180.83
cm-1, 574.35 cm-1, and 525.11 cm-1 were
observed (Figure 6 on the following page). The peaks at 2384.48
cm-1 and 2349.79 cm-1 are due to impurities and are
characteristic of all spectra produced on this instrument. They appeared when
a sample of KBr was run against a KBr background. The peaks at 1426.96
cm-1, 1180.83 cm-1, 574.35 cm-1, and 525.11
cm-1 correspond to the previously observed peaks for C60
of 1428.9 cm-1, 1181.2 cm-1, 576.3 cm-1, 527.3
cm-1. (Cox, et al. 2940-2944) These peaks in the fingerprint
region are due to specific vibrational motions which cause the shifting dipoles
within the C60 molecule.
An
original solution was prepared from 12.3 mg of C60 in 10 mL
tolulene. This was too concentrated to produce a usable absorbtion spectrum.
A 10 to 1 dilution was made which was still too concentrated. After another 10
to 1 dilution, a viable spectrum was produced. A primary peak was observed at
336.0 nm with an absorbance of 0.95065. A secondary peak was observed at 284.0
nm with an absorbance of 0.68556 (see Figure 7).
The
IR spectrum for the product of C60 and cyclopentadiene displayed
peaks at 3482.57 cm-1, 3417.75 cm-1, 3207.91
cm-1, 3098.44 cm-1, 2961.78 cm-1, 2918.88
cm-1, 2849.80 cm-1,
1558.71 cm-1, 1449.06
cm-1, and 1384.20 cm-1 (see Figure 10 on the following
page). The peaks at 3482.57 cm-1 and 3417.75 cm-1 are
indicative of the presence of moisture in the sample or the KBr. The peaks at
2961.78 cm-1, 2918.88 cm-1, and 2849.80 cm-1
fall within the region for carbon-hydrogen alkane bond stretching, and the peak
at 1384.20 cm-1 falls within
the carbon-hydrogen bond bending
region. These peaks are slightly shifted relative to the
peaks revealed in
these regions by the spectrum of straight cyclopentadiene (at 2964.81
cm-1, 2930.13 cm-1, and 2899.86 cm-1). The
peaks at 3098.44 cm-1 and 3207.91 cm-1 lie within the
carbon-hydrogen alkene bond stretching region. Similarly, the spectrum for
straight cyclopentadiene showed a peak in this region at 3044.47
cm-1. The spectrum for straight cyclopentadiene (Figure 8)
displayed a peak at 1364.63 cm-1 in the region characteristic of
carbon-carbon alkene bond bending; in this region the spectrum for the product
revealed peaks at 1558.71 cm-1 and 1449.06 cm-1. No
C60 peaks were displayed in the fingerprint region; several other
peaks were revealed between 1325.85 cm-1 and 461.93 cm-1.
This indicates that the cage stretching for the fullerene was altered due to
the addition of the cyclopentadiene.
A
sample was made by dissolving a portion of the C60-cyclopentadiene
product in toluene. This sample was run through the UV-Vis against a toluene
blank and the resulting spectrum showed peaks at 284 nm and 331 nm with
absorbances of 0.71488 and 0.41072, respectively
(Figure 11). The peak at
331 nm was less intense than that at 284 nm. Furthermore, the intensity of the
peak at 331 relative to the peak at 294 was small compared to that for the pure
C60. This also indicates a change in conjugation and indicates that
a reaction occurred.
The
IR spectrum for the C60-piperylene displayed peaks at 3037.70
cm-1, 2955.37 cm-1,
2924.32 cm-1, 2837.50
cm-1, 1449.83 cm-1, 1427.12 cm-1, 1360
cm-1, 1181.06 cm-1, 724.38 cm-1, and 525.28
cm-1. The peaks at 2955.37 cm-1, 2924.32
cm-1, and 2837.50 cm-1 correspond to the region for
carbon-hydrogen bond stretching, and the peak displayed at 1360 cm-1
indicates carbon-hydrogen alkane bond bending. Peaks in these regions were
revealed by the spectrum for straight piperylene at 2918.49 cm-1,
2855.13 cm-1, and 1434.26 cm-1. The peaks displayed
at 3037.70 cm-1 and 724.38 cm-1 indicate
carbon-hydrogen alkene bond bending and stretching; the spectrum for straight
piperylene revealed peaks in these regions at 3087.08 cm-1,
3011.06 cm-1, 1000.88 cm-1, and 899.01
cm-1. The peak corresponding to the region for carbon-carbon alkene
bond stretching was displayed at 1449.83 cm-1; the peaks in this
region displayed by the spectrum for straight piperylene were those at 1653.72
cm-1 and 1601.72 cm-1. The peaks shown in the
fingerprint region at 1427.12 cm-1, 1181.06 cm-1 and
525.28 cm-1, as well as the carbon-carbon alkene peak at 1449.83
cm-1 may indicate alteration in the fullerene cage stretching. It
is also possible that an excess of the C60 reagent was present in
mixture with the product (Figure 14 on the following pages).
A
portion of the C60-piperylene product was dissolved in toluene and
alalyzed with the UV-Vis. Peaks at 284 nm and 332 nm were observed with
absorbances of 0.81004 and 0.39722, respectively. As can be seen, the first
peak has a much higher intensity than the peak at 332 nm, indicating a drop in
conjugation between the pure C60 and the C60-piperylene
product. This verifies that a reaction did take place between piperylene and
C60 (Figure 15).
The
IR spectrum for the C60-toluene product displayed peaks at 3018.69
cm-1, 2917.09 cm-1, 2858.93 cm-1, 1507.64
cm-1, 1456.82 cm-1, 1419.80 cm-1, 1183.24
cm-1, 1020.33 cm-1,
809.06 cm-1, 577.51
cm-1, and 527.14 cm-1. The peaks displayed at 1419.80
cm-1,
1183.24 cm-1, 1020.33 cm-1, 577.51
cm-1, and 527.14 cm-1 correspond to the peaks shown in
the spectrum for straight C60, indicating that a portion of the
C60 reagent did not react and was left in the final product mixture.
The peaks at 2917.09 cm-1 and 2858.93 cm-1 fall within
the region for carbon-hydrogen alkane bond stretching, and the peak at 1456.82
cm-1 is indicative of alkane bond bending. Peaks were displayed in
these regions at 2929.34 cm-1, 2871.14 cm-1, 1451.38
cm-1 for straight toluene. The peak displayed at 3018.69
cm-1 is within the carbon-hydrogen aromatic bond stretching region,
and the peak at 809.06 cm-1 indicates aromatic bond bending. The
spectrum for straight toluene revealed peaks at 3026.83 cm-1 and
728.03 cm-1,
n the aromatic bond regions. The peak shown at
1507.64 cm-1 lies within the region for
carbon-carbon aromatic
bond stretching; straight toluene displayed a peak in this region at 1495.07
cm-1. The presence of these peaks lends support to the assumption
that toluene has bonded with C60 (Figure 18).
A
portion of the C60-toluene product was dissolved in toluene for
analysis. The resulting spectrum revealed peaks at 285 nm with an absorbance
of 0.47909 and 333 nm with an absorbance of 0.26501. The peak at 333 nm is
less intense than that at 285, while in the straight C60 UV-Vis, the
peaks are nearly equal in intensity, with the peak at 285 nm even being
slightly less intense than that at 333 nm. This indicates that a reaction
occurred, resulting in less conjugation in the product than in straight
C60 (Figure 19 on the following page).
Upon
analysis of the C60-ferrocene product five main peaks were observed.
They were at
3414 cm-1, 3092 cm-1, 2917
cm-1, 2847 cm-1, and 1507 cm-1. The peak at
3414 cm-1 is due to a small amount of water in the KBr pellets or
in the sample. The peaks at 2917 cm-1 and
2847 cm-1
are within the carbon-hydrogen bond stretching region in alkanes. The peak at
3092 cm-1 is also characteristic of a carbon-hydrogen stretch,
only in aromatics. At 1507 cm-1, the peak is characteristic of a
carbon-carbon double bond stretch. This peak is characteristic of aromatics as
well. Upon comparison with the IR's for straight C60 and pure
ferrocene, many similarities are evident with each. The peak at 3092
cm-1 corresponds to the peak at 3093 cm-1 on the
ferrocene IR. There is also a band around 1600 cm-1 on each
spectrum that corresponds to carbon-carbon double bonds in aromatic compounds.
Within the fingerprint region of the spectrum, there are peaks at 1427
cm-1, 1181 cm-1, 575 cm-1, and 525
cm-1 which correspond to those observed for straight C60
at 1426 cm-1, 1180 cm-1, 574 cm-1, and 525
cm-1, respectively. If the product was pure it would be expected
for these peaks to be shifted slightly from the spectrum for straight
C60. In this sample, no shifting is evident, indicating that there
is some unreacted C60 mixed in with the product. It is also
possible that there is a mixture of three or more products (Figure 22).
UV-Vis
analysis of the C60-ferrocene product in toluene produced two peaks.
The first at 284 nm, and the second at 335 nm. The relative intensities of
these peaks are similar to that for pure C60 in toluene. This goes
against what would be expected according to both the IR and NMR for the
C60-ferrocene product (Figure 23 on the following page).
After doing the IR and UV-Vis spectra, it was realized that no product was formed, so no proton NMR was run.
Upon
analysis of the C60-bromobenzene product peaks at 1427
cm-1, 1181 cm-1, 574 cm-1, and 525
cm-1 were observed. These peaks directly correspond to the
cage-stretching peaks for straight C60 indicating that no reaction
took place between the C60 and bromobenzene
(Figure 26).
Upon
analysis of the C60-bromobenzene product dissolved in toluene, peaks
similar to those displayed by straight C60 were observed. Peaks
were displayed at 286 nm and 336 nm, leading to believe that no reaction
occurred (Figure 27).
IR
analysis of the C60-aniline product revealed peaks at 1427
cm-1, 1181 cm-1, 575 cm-1, and
525
cm-1. As with the bromobenzene product, these peaks directly
correspond to the cage stretching peaks for pure C60, indicating
that no reaction took place (Figure 30 on the following page).
Analysis
of a portion of the C60-aniline product in toluene revealed peaks at
284 nm and
336 nm. They are similar in appearance to those observed for
the straight C60 UV-Vis, indicating that no reaction took place
(Figure 31).
