ESI mass spectrometry was undertaken on the black powder samples beforehand but
because most PAHs do not contain groups to be ionised easily they are not observed.
Therefore, a different method was developed by using the published work of
Simpson et al. where a solid sample was attached onto a MALDI plate and the
readings measured in this way.169 With this type of direct ionisation of a sample the
mass readings were not particularly accurate, but did suggest structures for species
which could have been formed.
The mass spectrometry results for the pyrene derived black solid product are below.
There were also a number of unidentified peaks but these were probably those that
did not cyclise fully and can have different substituents on the side chains. In
addition, the mass spectrometry results can also provide information concerning the
m/zobserved m/z of possible compound
Possible compound (Only one isomer drawn)
328.0635 328.0888 350.0837 350.1096 402.0903 402.1045 424.1134 424.1252 477.1420 476.1201 551.1640 551.1430 825.2073 825.1849
The first three compounds in Table 2 (at m/z 328, 350 and 402) were also detected
by the AFM as the images can be seen above (Figure 73).
The anthracene and perylene derived samples were also similarly analysed (Table 2
& 3).
m/zobserved m/z of possible
compound
Possible compound (Only one isomer drawn)
327.157 327.1168
343.177 343.1117
363.212 363.1179
379.237 379.1123
Table 2: Mass spectrometry results from anthracene derived black powder, where proposed structures are drawn in accordance with the mass observed; anthracenem/zpeaks were
m/zobserved m/z of possible compound
Possible compound (Only one isomer drawn)
363.001 363.1179 379.017 379.1117 400.048 400.1252 327 417.077 417.1274 438.100 438.1409 512.174 512.1565
Table 3: Mass spectrometry results from perylene derived black powder, where proposed structures are drawn in accordance with the mass observed; perylenem/zpeaks were detected
3.10
Summary
The peri-condensation reactions on naphthalene, anthracene, pyrene and perylene
produced numerous products due to poly-annulation, which were purified and
characterised. The glycidol units can add onto PAHs which contain peri positions
multiple times rather than only once, with the increasing ring sizes being harder to
form. Pyrene has been observed to react to produce products with up to seven
additional rings. Where not all the cyclisations are completed, side chains can
remain. A mechanism was proposed in relation to the Skraup-Doebner von Miller
quinolone synthesis, where experiments including 13C3 carbon labelling were
conducted to help support this. This has yielded better understanding of the reaction
and thus, the characterisation of the black solid product has now been completed
which was of unknown chemical composition.
STM/AFM was utilised successfully where other analytical methods failed to help
characterise unknown compounds especially those which were difficult to dissolve in
common organic solvents. Hopefully STM/AFM can be used more regularly in the
future for the characterisation of difficult compounds which may be difficult to
4 Chapter 4: Synthesis of triangulene
4.1
Introduction
Having synthesised and imaged the benzo[cd]pyrene radical by means of
AFM/STM, we would attempt to image triangulene 10. This would require the
abstraction of two hydrogens from the parent dihydro-triangulene12 rather than one
to form the reactive diradical (Scheme 70).
Scheme 70: Abstraction of two hydrogens from dihydro-triangulene 12 to form triangulene 10.
The potential existence of triangulene10can be dated back to 1941 when it was first
discussed by Clar and thus, it is commonly known as Clar’s hydrocarbon.387 This
D3h-symmetric compound is the smallest triplet ground state polybenzenoid and due
to its arrangement it is impossible to draw a Kekulé structure.388Triangulene’s open-
shell triplet ground-state is an estimated 20 kcal mol-1 lower than its singlet state.29,
389 Thus, it is of great interest to many material scientists for its use in organo-
electronics, since this field attempts to exploit spin and molecular electronics of such
compounds.389, 390Triangulene10 is part of a triangular shaped series of PAHs with
Figure 76: The triangular series of graphene fragments which due to their structure, do not have a singlet ground-state. The first structure is the phenalenyl radical 7 and the second is the
triangulene diradical 10.
Triangulene10is yet to be isolated due to its open-shell nature it is considered to be
highly reactive and unstable.29, 387-390 Clar could not isolate triangulene, although he
synthesised numerous derivatives. Others have attempted but have only been able to
form substituted and more stable triangulenes. Clar attempted to form triangulene by
many synthetic methods with one of his shorter routes summarised in Scheme 71.316,
391 In the last step where 1,2,3,5,6,7-hexahydro-dibenzo[cd,mn]pyrene 342 was
dehydrogenated, Clar reported that during the reaction 4,8-dihydro-4H,8H-
dibenzo[cd,mn]pyrene12was observedviaUV spectroscopy. However, at the end of
the reaction a brown solid was obtained with a very small quantity of the starting
material persisting and nothing else identifiable.316 With this result, Clar concluded
that triangulene 10 was probably generated but because of its instability and high
reactivity it polymerised immediately and therefore he was unable to isolate it.316, 392
Clar proceeded with further work in this area, predominantly working to produce
different derivatives with the core of the triangulene structure in attempts to
understand these compounds further and to identify a different synthetic route to
triangulene.316, 393 Unfortunately Clar was unable to isolate triangulene with the
Scheme 71: One of Clar’s first synthetic attempts to form triangulene 10.316, 391
The next significant step in triangulene chemistry was completed by Hara et al. in
1977 where they were able to successfully obtain the triangulene dianion 13 with
anion was then quenched in D2O adding two deuteriums; one at each dihydride site
producing species343as confirmed by mass spectrometry.26
Scheme 72: The formation of the dianion 13 by Haraet al.with NMR spectroscopy confirmation.
In the 1990s Allinson et al.were interested in making non-Kekulé PAH radicals for
the potential use as organic molecular magnets.134, 388, 394, 395 A number of structures
were considered with one of the frontrunners being triangulene 10. Allinson et al.
reported the first synthesis of a stable tri-substituted triangulene derivative, the
Scheme 73: Allinsonet al.synthetic route to a stable trioxytriangulene derivative 349.134, 388, 395
The synthesis of this triplet state trioxy derivative was similar to the synthetic route
of Clar but most of the more hazardous reagents were substituted with more
contemporary reagents.388 The trioxytriangulene derivative 349 was analysed by
formed to mimic similar electronics to triangulene although it is stabilised by the
three tert-butyl groups. These groups were chosen as they would provide the least
effect in terms of electronics when compared to heteroatoms such as oxygen which
were used by Allinsonet al.29, 388ESR was used to detect the diradical triplet ground
state of the tri-tert-butyl triangulene species350.29
Figure 77: Tri-tert-butyl triangulene species 350 synthesised by Inoueet al.29
Since the 1950s triangulene has been of interest to many scientists especially due to
its potential use in material science, but due to its instability it has yet to be isolated
in the triplet form without any stabilising substituents.