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.)