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This document is downloaded from DR‑NTU (https://dr.ntu.edu.sg)Nanyang Technological University, Singapore.
Coordinative Polymers with Fullerene : ExploringSynthesis and Potential Applications
Ooi, Eric Chong Yih
2016
Ooi, E. C. Y. (2016, March). Coordinative Polymers with Fullerene: Exploring Synthesis andPotential Applications. Presented at Discover URECA @ NTU poster exhibition andcompetition, Nanyang Technological University, Singapore.
https://hdl.handle.net/10356/84140
© 2016 The Author(s).
Downloaded on 06 Aug 2021 04:23:00 SGT
Corannulene-Thiophene Oligomers#
1. Juríček, M.; Strutt, N.L.; Barnes, J.C.; Butterfield, A.M.; Dale, E.J.; Baldridge, K.K.; Stoddart,
J.F.; and Siegel, J.S. 2014. Nature Chemistry, 6, pp. 222-228.
2. Mack, J.; Vogel, P.; Jones, D.; Kaval, N.; and Sutton, A. 2007. Org. Biomol. Chem.,5, pp.
2448-2452.
3. Zabula, A.V.; Spisak, S.N.; Filatov, A.S.; Rogachev, A.Y.; Cléracde, R.; and Petrukhina, M.A.
2016. Chem. Sci, Advance Article.
4. Lawton, R.G.; Barth, W.E. 1971. J. Am. Chem. Soc., 93 (7), pp. 1730-1745.
5. Butterfield, A.M.; Gilomen, B.; and Siegel, J.S. 2012. Org. Process Res. Dev., 16 (4), pp. 664-
676.
Reference
Dendrimeric Corannulenes*
Fig 7: Design of the synthesis route for a new corannulene-based motif. High number of corannulene in
close proximity is expected to equip the molecule with competency to complex with other
macromolecules.
Corannulene Architechture: Dendrimer and Extended π Conjugation
Corannulene, being a fraction of a fullerene, has strong potential to be an outstanding
monomer in providing superior properties to a conjugated polymer. This study aimed
to establish the first of its kind synthetic strategy for corannulene-contained
oligomers and characterise its chain-length-properties relationship. The information
generated in the study can be particularly useful for future discovery of corannulene-
contained oligomer’s applications and for understanding corannulene-conjugated
polymer’s behaviour.
Category: Physical and Biological Sciences Student: Ooi Chong Yih, Eric Project ID: SPMS15024School of Physical and Mathematical Sciences
Project Title: Coordinative Polymers with Fullerene: Exploring Synthesis and Potential ApplicationsSupervisor: Asst Prof Mihaiela Stuparu
URECA
Undergraduate Research Experience on CAmpus
www.ntu.edu.sg/ureca
Corannulene is known to have outstanding photoelectronic properties and is able to
be a good π-acceptor[3]. In this study, we would like to investigate the interaction of
corannulene, as a π-acceptor, with different kind of aromatic donors, through various
spectroscopic techniques.
Corannulenre Donor-Acceptor͌§
Fig 8: Synthetic strategy for creating the species of interest.
Fig 9: A solvent-dependent absorption and emission was observed during our primary examination. [1]
Corannulene-donor species in toluene (starting from the left), hexane, chloroform, acetonitrile and
DMSO (i.e. right most). [2 & 3] UV-VIS absorption and fluorescence emission of the corannulene-
donor species in the respective solvent.
300 350 400 450
0.0
0.2
0.4
0.6
Ab
so
rba
nce
Wavelength(nm)
Toluene
Hexane
Chloroform
Acetonitrile
Dimethyl Sulfoxide
400 450 500 550
0
100
200
300
400
500
600
Flu
ore
sce
nce
In
ten
sity
Wavelength (nm)
Toluene
Hexane
Chloroform
Acetonitrile
Dimethyl Sulfoxide
1 2 3
Corannulene§
Corannulene, C20H10, features several exciting characteristics that
has received much attention since its discovery. One of them being
that it is the smallest fullerene fragment that has retained its
curvature. Thus, begging the question – is this extensively
conjugated molecule aromatic (figure 2)? Additionally,
corannulene’s host-guest interaction with macromolecules[1], its
self-assembly behavior and its photoelectronic properties[2] are of
Fig 2: [1] Corannulene possesses non-planar geometry that resembles the fullerene. [2] However,
corannulene behaves and reacts similarity to how any aromatic species does. A bi-concentric conjugation
model that comprises of cyclopentadienyl core and cyclopentadecaheptaenyl periphery is believed to be
responsible to corannulene’s aromaticity[3,4].
1 2
Fig 1: Corannulene
much interest as well. In light of the interesting features of corannulene, this project
started off with the synthesis of this fascinating molecule (figure 3) and aspired to
construct corannulene into different architectures in subsequent studies.
Fig 3: The synthesis of corannulene developed by Butterfield et. al.[5] with a slight modification.
Fig 4: Corannulene-Thiophene oligomers can be attained though systematic synthesis.
300 400 500 6000.0
0.1
0.2
0.3
0.4
0.5
Absorb
ance
Wavelength (nm)
Single unit
Dimer
Trimer
Tetramer
400 450 500 550 600 650
0
10
20
30
40
50
60
70
80
90
100
110
120
Inten
sity (
a.u.)
Wavelength (nm)
cap
dimer
trimer
tetramer
Single unit
Dimer
Trimer
Tetramer
Flu
ore
sce
nce
Em
issi
on
Wavelength(nm)
Fig 8: [1, 2, 5 & 6] Dimer (n = 0, left), trimer (n = 1, middle) and tetramer (n = 2, right) of corannulene-
thiophene oligomer. [1 & 2] Solid state corannulene-thiophene oligomers under visible and UV light. [3
& 4] UV-VIS absorption and fluorescence emission of the respective corannulene-thiophene oligomers
in dichloromethane. [5 & 6] Dissolved corannulene-thiophene oligomers, in dichloromethane, under
visible and UV light.
1
2
3
4
5
6
AcknowledgementI would like to extend my highest gratitude towards the patient guidance of my supervisor (Asst. Prof.
Mihaiela Stuparu*) and mentors (Dr. Ji Li#, Dr. Sivaramapanicker Sreejith͌, and Dr. Venkatachalam
Rajeshkumar§); also all the assistance rendered by fellow researchers (Dr. Surendra Mahadevegowda,
Kristina Sorochkina, Zhang Zhuang, Lee Yuan Theng, Goh Tong Yin and Ang Min Hui.)