European Polymer Journal 65 (2015) 414

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Feature Article

Polymer compatibilized self-assembling perylene derivatives

Elianne Dahan, Pudupadi R. Sundararajan
Department of Chemistry, Carleton University, 1125 Colonel By Drive, Ottawa, Ontario K1S 5B6, Canada

MACROMOLECULAR NANOTECHNOLOGY

a r t i c l e

i n f o

Article history:
Received 20 October 2014
Received in revised form 13 November 2014
Accepted 16 November 2014
Available online 27 November 2014
Keywords:
Fluorescent gel
Nanostructure
Perylene tetracarboxy diimide
Polystyrene
Poly (dimethyl siloxane)
Phase separation

a b s t r a c t
Solution coating of functional small molecules in polymer lms is a convenient approach to
fabricating exible optoelectronic and photo-functional devices. Uniform dispersion of the
small molecule in the polymer and inhibition of aggregation are requirements for the
robust functioning of the devices. Alternate approaches such as incorporating the functional molecule as part of the polymer chain have been examined, although such methods
limit the exibility in materials choice. While perylene or perylene tetracarboxy diimide
(PTCDI) or perylene imide (PI) phase separate into discrete crystals in polymer lms, we
nd that functionalizing the perylene imide with a polymer or oligomer segment that is
compatible with the host polymer matrix results in highly uniform dispersion of the small
molecule, with the inherent photophysical properties of the perylene segment unaffected.
We demonstrate this approach with oligostyrenePTCDIoligostyrene dispersed in
polystyrene, PDMSPI and PDMSPTCDIPDMS in PDMS in solution cast lms and in
two-component gels from organic solvents. Fluorescent gels of polystyrene and PDMS
(without crosslinks or functionalization) were obtained via this route.
2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

Contents
1.
2.
3.

4.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.
Morphology of the composite films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2.
Optical properties of the composite films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3.
Composite gels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.4.
Morphology of the composite gels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.5.
UVVis and fluorescence spectra of the composite gels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Appendix A. Supplementary material. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1. Introduction
Corresponding author.

Dispersing functional small molecules in polymer matrices is a common approach to fabricating organic-based

E-mail address: Sundar@Carleton.ca (P.R. Sundararajan).

http://dx.doi.org/10.1016/j.eurpolymj.2014.11.022
0014-3057/ 2015 Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

exible devices, the earliest examples being the reprographic photoreceptors and polymer-dispersed liquid
crystal displays [16]. Solution coating of functional multilayers using such compositions are preferred for exible
devices. The relative concentration of the functional
molecule often has to be as high as 50 wt% in the polymer.
For example, Santerre et al. [7] reported the properties of
OLED devices based on N,N0 -diphenyl-N,N0 -bis(3-methylphenyl)-[1,10 -biphenyl]-4,40 -diamine (TPD) dispersed in
polymers with high Tg. The best performance was obtained
with a TPD concentration of 75%. Detailed studies have
been reported on the morphologies resulting from phase
separation of three different charge transport molecules
in polycarbonates and polystyrene [811]. Molecular dispersion of the small molecule is essential and any phase
separation and crystallization would lead to degradation
of the device performance. Smith et al. [12] have shown
that crystallization of TPD was the cause of delamination
of an OLED device. Scharfe [13] discussed the effect of such
crystallization on charge trapping in photoreceptors. The
leaching of the transport molecule would be more prevalent in copiers and printers using liquid developers.
As an alternate to dispersing the functional small molecule in polymer matrices, Limburg et al. [14] and Ong et al.
[15] designed arylamine based polymers and copolymers
by incorporating the photoactive molecules as part of the
chain to prevent phase separation. Design and properties of
several such polymers with arylamine functionality in the
main chain or side chain have been studied [1618]. Conjugated polymers for solar cell applications have also been
examined [19,20]. All-polymer bulk hetero-junction solar
cells using blends of polymers bearing donor and acceptor
moieties have been reported by Jenekhe et al. [21]. The
advantage of using a functional molecule dispersion in a host
polymer is that either can be changed at will, whereas a specic polymer with the functional segment cannot.

Perylene and its derivatives have been investigated over

the past few decades for their applications in optoelectronic and photovoltaic devices [22,23]. The classic crystallographic investigations by Hdicke and Gracer [24]
related the effect of substituents on the p-overlap and
the color. The self-assembly facilitated by the p-interaction
can be modulated by substitutions at the imide nitrogen as
well as the bay positions [2527]. Linear and dove-tail
substitutions have been used to create nano-ber morphologies [28,29]. Supramolecular association between
melamine functionalized perylene tetracarboxylic diimide
(PTCDI) and cyanuric acid via hydrogen bonding resulted
in nano-ribbon and nano-rope morphologies [30]. The
applications of perylene imides and diimides in solar cell
and organic electronics have been summarized in recent
reviews [31,32].
When perylene (or PTCDI) by itself was dispersed in a
polymer matrix, the small molecule formed discrete crystals of a few microns as shown in Fig. 1, irrespective of
the solvent used for casting the lms. We discussed the
self-assembly of PTCDI substituted with oligostyrene on
both imide nitrogens (PSPTCDIPS, Scheme 1a) in solution
[33] as well as in the gel state [34]. In another study, we
substituted poly (dimethyl siloxane) (PDMS) on both imide
nitrogens (Di-PDMS) (Scheme 1b) or on one (Mono-PDMS)
(Scheme 1c) and reported on the differences in the morphology of the mono and di-substituted PTCDI in solution
[35,36] and gels [37]. Both PSPTCDIPS and Di-PDMS are
non-ionic Gemini surfactants. We believed that by attaching an oligomeric or polymeric chain which is compatible
with the host polymer, the mixing of such compatibilized
PTCDI would be better, and a uniformly dispersed
composite lm could be obtained. For example, with oligostyrene attached to PTCDI, we expect that a good dispersion
in polystyrene (Scheme 1d) could be achieved. In the present work, we dispersed PSPTCDIPS in the corresponding

Fig. 1. OM of solvent cast lms of (a) perylene/polystyrene (5/95 wt%), (b) PTCDI/polystyrene (5/95), (c) perylene/polycarbonate (2/98), (d) perylene/
polycarbonate (5/95) and (e) perylene/PMMA (2/98). Tetrachloroethylene was used for (e) and chloroform for the others.

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E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

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E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

Scheme 1. (a) PolystyrenePTCDIpolystyrene Gemini surfactant, (b) PDMSPTCDIPDMS Gemini surfactant, (c) inverse macromolecular surfactant PDI
PDMS, (d) polystyrene and (e) PDMS.

polymer, polystyrene (PS), in an attempt to make composite polymer lms. We also prepared gels of PSPTCDIPS
recently, with trans-decalin [34]. Since this solvent has
been used in the past for gelation involving polystyrene,
we prepared two-component composite gels with different
concentration of PSPTCDIPS in polystyrene. In our previous work, we used propylamine for gelation of Mono- and
Di-PDMS [37]. This solvent was also used for gelation with
PDMS without having to crosslink or functionalize the
polymer [38]. In the present work, we prepared PTCDI
dispersed gels of PDMS with different concentrations of
Mono- or Di-PDMS. The optical properties of the selfassembled polymer-compatibilized PTCDI remained the
same upon dispersion in the corresponding polymer matrices.
2. Experimental
The syntheses of Mono-PDMS and Di-PDMS have been
described in our previous publications [35,36]. PSPTCDI
PS was synthesized as described by Islam and Sundararajan
[33]. Poly (dimethylsiloxane) (Mw = 182,600; Mn = 106,000,
CASRN 9016-00-6), polystyrene (Mw = 239, 700 and

Mn = 119, 600) and all the solvents (propylamine, chlorobenzene, THF, or chloroform of laboratory grade) were purchased from Aldrich Chemical Company. Solvent cast lms
were prepared by dissolving appropriate mixtures of
PSPTCDIPS and PS in chlorobenzene, THF, or chloroform.
Relative concentrations of 1, 5 or 10 wt% of PSPTCDIPS in
PS were used. Films were coated on a glass substrate using
an electrically driven lm coater and were dried at a
very low rate of the solvent evaporation at ambient conditions for 24 h and then under vacuum for 24 h. The nal
thickness of the lms was about 20 lm.
Gelation studies on PSPTCDIPS (a Gemini surfactant)
were discussed in our previous publication [34]. In the
present work, PS/PSPTCDIPS composite gels were prepared with 210 wt% of PSPTCDIPS in PS. A total solute
concentration of 0.8 mM was dissolved in trans-decalin
at temperatures ranging from 78 to 82 C with constant
stirring. This resulted in a red solution. Closed vials were
used to avoid the evaporation of the solvent. The gels were
prepared by slow cooling the solution and as a quick test,
gelation was conrmed by tube inversion, i.e., no owing
solvent.

E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

indium and tin as certied reference materials. DSC traces

for lms were recorded with about 8 mg of the samples
under the ow of nitrogen. UVvisible absorption spectra
were recorded using a Varian CARY 3 UVVis spectrophotometer. The data were processed with CARY WinUV Software version 3.00. The uorescent emission data were
collected using a Varian CARY Fluorescence spectrophotometer at the excitation wavelengths (kex) of 460 nm
and 417 nm with a bandwidth of 5 nm for excitation and
5 nm for emission. Data collection and processing were
done by Eclipse WinFLR Software (version 1.1).
3. Results and discussion
3.1. Morphology of the composite lms
While perylene, without any substitution, would form
crystals, attaching short chains to perylene mono- or diimide leads to vesicular, nano-web or nanowire morphology
when precipitated from solution or during gelation. Fig. 1
shows the optical micrographs (OM) of lms cast from chloroform or TCE solutions of polystyrene, polycarbonate or
PMMA with low concentrations of perylene or PTCDI. Even
in the presence of the polymers, large, discrete crystals of

Fig. 2. OM images of PS/PSPTCDIPS lms (top: 1 wt% PSPTCDIPS) and (5 wt% PSPTCDIPS) cast from (a, d) chlorobenzene, (b, e) chloroform and (c, f)
THF. Spin cast lms with PS/PSPTCDIPS (95/5 wt%) in (g) chloroform and (h) THF are also shown.

MACROMOLECULAR NANOTECHNOLOGY

We reported the gelation with PDMS before, without

any crosslinks or functionalization [38], as well as the gelation of Mono-PDMS and Di-PDMS [37]. In the present study,
a solute concentration of 0.1 M (18.26 g/L) in propylamine
was used, with 2%, 5%, or 10 wt% Mono-PDMS and 5%,
10 wt% Di-PDMS in PDMS. Solutions were prepared with
constant stirring at temperatures ranging from 65 to
75 C. Gels were then prepared by slow cooling to room
temperature by turning off the hot plate. Gels were prepared in closed vials to avoid the evaporation of the solvent.
Gelation was tested by tube inversion with no owing
solvent.
The optical micrographs (OM) were recorded using a
Zeiss Axioplan polarized optical microscope in transmission mode. Northern Eclipse (version 6.0 and 8.0) image
processing software was used to record the images. Scanning electron microscopy (SEM) images were obtained
using a VEGAII XMU (TESCAN, Czech Republic) scanning
electron microscope. Dry samples were sputter coated
with 80:20 Au/Pd target using a Hummer VIII Sputtering
System (Anatech Ltd., Alexandria, VA). Thermal analysis
was performed using a TA Instruments 2010 differential
scanning calorimeter at 10 C/min heating rate. The instrument was calibrated for temperature and energy with

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E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

Fig. 3. SEM images of lms with 5 wt% PSPTCDIPS (ac) and 10 wt% PSPTCDIPS (d,e) using (a) chlorobenzene, (b) chloroform and (c) THF, (d)
chlorobenzene, (e) chloroform.

the small molecules are seen in all these cases. Fig. 2 shows
the OM of lms of PSPTCDIPS in polystyrene, cast from
three different solvents. Spherical domains, with almost
uniform size are seen with lms cast from chlorobenzene
and chloroform. Especially with a 5 wt% concentration in
chloroform (Fig. 2(e)), dense spheres with uniform size are
seen. Such close packed morphology ensures that percolation threshold has been reached and would facilitate charge
hopping. The lms made with THF, however, do not show
discrete domains (see Optical Properties below). The length
of the oligostyrene chain attached to PTCDI in this case is
only about 12 units. The molecular weight of the polystyrene matrix is over 100,000. With the oligostyrene attachment, single crystals of perylene is not seen in the
polystyrene matrix. We have shown previously that
drop-cast lms of PSPTCDIPS show vesicular and fused
vesicular morphologies [33]. Such spherical morphology is
maintained when this Gemini surfactant is dispersed in
polystyrene. Fig. 2(g) and (h) shows spin cast lms with
chloroform and THF. A highly uniform spherical morphology is seen in these lms. With the oligostyrene segment
dispersed in the polystyrene matrix, the domain formation
is due to the self-assembly of PTCDI. Thus it is a supramolecular solution.
Fig. 3 shows the SEM images of lms with 5 wt%
PSPTCDIPS in polystyrene. No domains similar to those
in Fig. 2(a), (b), (d) and (e) are seen in Fig. 3(a) and (b)
which would indicate that the domains seen in Fig. 2 are

sub-surface. We have reported such a phenomenon before

in the case of a functionalized phthalocyanine dispersed in
polycarbonate or PMMA [39], as well as biscarbamates dispersed in polycarbonate [40]. In another study [41], we
described a polymer dispersed self-assembling small molecule system, in which a homologous series of carbamates,
with a hydrogen-bonding moiety and alkyl side chains,
was dispersed in polycarbonate. These self-assembling
molecules formed colloidal size domains in the polymer,
which involved a hierarchy of three levels of assembly.
When a lm is cast from solution, the self-assembly of
these small molecules is so rapid that they form domains
in the bulk of the polymer during solvent evaporation
and do not diffuse to the surface of the polymer lm. Due
to the sub-surface assembly, no domains are seen in the
SEM images, although their presence is seen in the transmission OM. Fig. 3(c) shows that with THF, spherical
domains of less than a micron are seen on the surface as
well. The SEM images of lms with a higher concentration
of 10 wt% PSPTCDIPS (Fig. 3(d) and (e)) show domains
on the surface as well, with those in Fig. 3(e) being of nanometer size. The highly monodisperse size of these domains
show that spontaneous nucleation occurs due to selfassembly in the polymer matrix. Fig. 4 shows the photographs of the polystyrene lms with 1, 5 and 10 wt% PTCDI.
Consistent with the OM observations, the lm is transparent with 1 and 5 wt%, becoming opaque with higher
concentration.

E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

The sub-surface self-assembly of the small molecules in

the polymer matrix has another advantage. Typically, the
charge transport layer (CTL) of a photoreceptor contains
the charge transport molecule (CTM) such as TBD, to a loading of about 50%. Such a high loading of CTM essentially
leads to a metastable composite. Abrasion due to brushcleaning of the photoreceptor after each copy/print cycle,
leaching due to the use of liquid developer etc., result in
the loss of the charge transport molecule (CTM) which
would change the composition of the active layer and hence
its performance. Over-coating the CTL with abrasion-resistant layers (such as siloxane) has been adopted as a route to
reduce the loss of the CTM [42]. Sundararajan et al. [43]
showed that introducing cyclodextrins in the CTL to form
polycarbonate/cyclodextrin rotaxanes reduced the abrasion signicantly. The use of a self-assembling molecule
such as PSPTCDIPS obviates the need for such add-on
coatings, since the active molecule is assembled sub-surface in the polymer matrix. An optimum concentration is
needed as well for such sub-surface morphology since
beyond a certain concentration of the small molecule,
domains are formed on the surface as well, as seen in
Fig. 3(d) and (e). In spite of the domains seen on the surface
of the lms, note that these are highly monodisperse in size
(nanometers) in the case of lms cast from chloroform
(Fig. 3(e)).
To address the question of whether a compatible oligomer is indeed required as a side chain to form such uniform
domains described above, we dispersed Mono-PDMS and

Fig. 5. The variation of glass transition temperature of polystyrene with

various concentrations of PSPTCDIPS using three different solvents.

Di-PDMS in polystyrene. As the PDMS segment and polystyrene are not miscible, the morphology shown in Fig. S1
(Supplementary data) was obtained. The dagger-like morphology in the OM shown in Fig. S1a is due to the fusion
of the vesicles of Mono-PDMS is the polystyrene matrix,
as seen in the SEM image in Fig. S1b.
As expected, the glass transition temperature (Tg) of
polystyrene was depressed as seen in Fig. 5. Although the
Tg was reduced from 104 C to about 80 C with 10 wt% of
PSPTCDIPS with the three solvents, the rate is different.
With the lms made with chlorobenzene and chloroform,
the Tg is reduced only by about 4 C with 5 wt% PS
PTCDIPS and the decrease is more pronounced thereafter.
However, with THF the decrease is linear, with the Tg reducing by 14 C, to 90 C with 5 wt% of PSPTCDIPS. The differences in the morphology and the thermal property
between the lms made with the three solvents do not
relate to the solubility parameter. However, it should be
noted that the viscosity of THF is 0.48 cP, while that of chlorobenzene and chloroform are 0.75 and 0.56 cP, respectively. The effect of the viscosity of the solvent on the
resulting morphology during self-assembly was discussed
before in our work on phthalocyanine aggregation in polycarbonate and PMMA matrices [39].

3.2. Optical properties of the composite lms

In our previous studies [37] on the self-assembly of
PSPTCDIPS in solution, the monomeric form of this compound in chloroform showed three distinct peaks at 456,
489 and 526 nm in the UVVis spectra, corresponding to
the S02, S01 and S00 transitions respectively. The
UVVis spectra in Fig. 6 shows that PSPTCDIPS in the
lm with PS cast from chloroform is in aggregate form,
with peaks at 498 and 532 nm, which are red-shifted1 with
respect to the solution spectrum. The lms from chlorobenzene also showed a red shit to 494 nm and 528 nm. In
addition, less intense peaks are seen in both Fig. 6(a) and
(b) at 564 and 589 nm with chlorobenzene and at 568 and
590 nm with chloroform, which could be assigned to the
aggregated state of PSPTCDIPS. However, when THF was
used as the solvent, the UVVis spectrum (Fig. 6(c)) showed
the monomeric form of PSPTCDIPS. The lm drop cast
from THF showed a major peak at 526 nm corresponding
to the S00 vibronic transition, a second peak at 491 nm corresponding to the S01 vibronic transition, and a hump at
1
For interpretation of color in Fig. 6, the reader is referred to the web
version of this article.

MACROMOLECULAR NANOTECHNOLOGY

Fig. 4. Transparency of the PS/PSPTCDIPS lms. L to R: 1, 5 and 10 wt% PTCDI in polystyrene, cast from chloroform.

MACROMOLECULAR NANOTECHNOLOGY

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E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

Fig. 6. UVVis absorption spectra of lms drop cast from different solvents at different PSPTCDIPS concentrations.

461 nm corresponding to the S02 vibronic transition. The

absorption spectra for the lms cast with chlorobenzene
and chloroform are broader which would indicate stronger
aggregation than that cast with THF. As discussed above,
there is a signicant difference in the morphologies of the
lms cast from the two chlorinated solvents and THF. The
latter did not show discrete domains in Fig. 2.
3.3. Composite gels
A recent review by Ajayaghosh et al. [44] summarized
the various p-system gels and their possible applications.
As we mentioned in our recent publication, there have been
a few studies on perylene diimide and phthalocyanine based
gels [26,4549]. The poor integrity and mechanical properties of these gels limit their applications. Incorporating them
in polymer matrices and fabricating two-component gels
might be a route to overcome these limitations. Such gels
in which the two components either do not have any specic
interactions or mutually complex are known [5054]. In the
present work, both polystyrene and PDMS are known to
form gels. We recently discussed the thermo-reversible
gelation of PSPTCDIPS, mono-PDMS and Di-PDMS. Hence,

we prepared the composite gels, in which the PTCDI bears

the compatible polymer segment in which it is incorporated.
Note that in contrast to the work of others, the three gelators
do not have C@O and NAH type hydrogen bonding groups in
their structure.
The dissolution and gelation onset temperatures of the
different composite gels are given in Table 1. The table
shows the effect of concentration of the oligomer-functionalized perylene in the corresponding polymer on the temperatures of dissolution and the onset of gelation. For
example with the PS/PSPTCDIPS composite gels that
were formed with trans-decalin at 5% PSPTCDIPS, a red
solution was obtained at 82 C. When the solution was
slow cooled, a deep red-colored, opaque and immobile
gel began to form at 57 C. However, when the concentration of PSPTCDIPS increases to 10 wt% PSPTCDIPS the
gelation onset of gelation drops to 50 C.
3.4. Morphology of the composite gels
We previously discussed that the morphology of PDMS
gels (without crosslinks or functionalization) consisted
of interconnected spherical domains, the Mono-PDMS gel

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E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

Table 1
The dissolution temperatures and onset of gelation of the different composite gels.
Composite gel

Solvent

%wt Concentration of oligomer

functionalized PTCDI (%)

Dissolution temperature (C)

Onset of gelation (C)

PS/PSPTCDIPS
PS/PSPTCDIPS
PS/PSPTCDIPS
PDMS/Mono-PDMS
PDMS/Mono-PDMS
PDMS/Mono-PDMS
PDMS/Di-PDMS
PDMS/Di-PDMS

Trans-decalin
Trans-decalin
Trans-decalin
Propylamine
Propylamine
Propylamine
Propylamine
Propylamine

2
5
10
2
5
10
5
10

78
82
79
65
68
66
65
63

53
57
50
55
59
58
55
53

gels, and so does polystyrene. The morphology of the composite gel consists of inter-meshed bers of polystyrene
and PSPTCDIPS, as seen in Fig. 8(c). These bers are
few hundred microns long and also fold along their length
to resemble an eaves trough, as seen in the higher magnication images in Fig. 8(d) and (e). This behavior was discussed in our previous work [34]. Fig. 8(g) shows the
uorescent polystyrene gel, with PSPTCDIPS in it.
3.5. UVVis and uorescence spectra of the composite gels
The absorption and uorescence spectra of the PS gels
with 2%, 5% and 10% PSPTCDIPS are shown in Fig. 9(a)
and (b). The absorption spectrum of the gel with 2%
PSPTCDIPS shows peaks at 500 and 535 nm with intensity
ratio I00/I01 of 0.97. There is a slight red shift of the of the
S00 peak, in the absorption spectrum with increasing concentration of PSPTCDIPS to 5% (503 nm, 546 nm) and
10% (504 nm, 548 nm) and the S00 peak increases in intensity signicantly. Such a change in the relative intensity of

Fig. 7. OM images of gels of PDMS with (a) 2%, (b) 5%, (c) 10% Mono-PDMS and (d) 5%, (e) 10% Di-PDMS. Photographs are shown for the following: (f)
PDMS + 5 wt% MonoPDMS gel, (g) emission color (kEx: 470 nm), (h) PDMS + 5 wt% DiPDMS gel, (i) emission color (kEx: 497 nm). (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this article.)

MACROMOLECULAR NANOTECHNOLOGY

forms vesicular morphology and the Di-PDMS gel forms

nano-bers. Fig. 7 shows the morphology of the composite
gels with PDMS/Mono-PDMS and PDMS/Di-PDMS.
Fig. 7(a)(c) shows that the spherical/vesicular individual
morphologies of PDMS and Mono-PDMS are maintained
in the composite gels. Both the Mono-PDMS and the DiPDMS self-assemble in the PDMS matrix, forming uniformly distributed spheres for Mono-PDMS and bers for
Di-PDMS. The spheres in the background of the gel blends
are due to the PDMS which has also been known to gel in
propylamine [38]. Note that the distribution of the
Mono-PDMS spheres and Di-PDMS bers are fairly uniform
in the polymer matrix, considering that the relative
concentration of the Mono- or Di-PDMS is no more than
10 wt% in the polymer. Fig 7(g) and (i) shows the photograph of the uorescent PDMS gel, with Mono or Di-PDMS
incorporated.
The morphology in the case of PS/PSPTCDIPS with
trans-decalin gel is shown in Fig. 8. As we discussed before,
PSPTCDIPS forms brillar morphology in trans-decalin

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12

E. Dahan, P.R. Sundararajan / European Polymer Journal 65 (2015) 414

Fig. 8. OM of polystyrene gels with (a) 5% and (b) 10% PSPTCDIPS; (ce) SEM images of polystyrene gels with (c) 2%, (d) 5%, (e) 10% PSPTCDIPS. (f) and
(g) show the color of the gel and the emission color (kEx: 503 nm), respectively. (For interpretation of the references to color in this gure legend, the reader
is referred to the web version of this article.)

Fig. 9. (a) UVVis and (b) uorescence spectra of PS with 2%, 5%, or 10% PSPTCDIPS.

the S00 peak with concentration was seen with the gels of
PSPTCDIPS by itself [34]. Fig 9(b) shows quenching of
the uorescence with increasing PSPTCDIPS concentration. This would indicate a higher order aggregation process
with higher concentration.
The absorption spectra (not shown here) of the PDMS/
5% Mono-PDMS gels showed peaks at 470, 495 and a
shoulder at 545 nm. This is nearly identical to the spectra
of pure Mono-PDMS gels in propylamine. The quenching
of uorescence intensity indicated stacking of the perylene
units in the gel state.

4. Conclusions
We have shown that dispersing oligomer functionalized
perylene imides in the corresponding polymers gives rise
to organized domains, without any change in the optical
properties. While perylene or perylene diimide by itself
will form single-crystal-like morphology when dispersed
in polymers, the oligomer attached to the imide nitrogen(s)
acts as a compatibilizer. Typically, concentration of 50 wt%
or more of the photo-conducting molecule (such as TPD) in
the polymer matrix is required for efcient charge

transport. However, both self-assembly and percolation

threshold were achieved with less than 10 wt% of the oligomer functionalized PTCDI in the corresponding polymers, while maintaining the transparency of the
composite lm. The concept of photoconductors with controlled aggregation was discussed by Dulmage et al. [55]
almost 36 years ago. In this paper we have shown that
polymer-compatibilized PTCDI enables creation of such
uniform morphology of self-assembled PTCDI segments.
It is also seen that the self-assembled structures develop
in the bulk of the polymer matrix, and are not seen on
the surface. This would be an advantage for exible polymer based devices. Although nano-wires and similar selfassembled morphologies have been reported with dovetail or hydrophilic/hydrophobic asymmetric substitutions,
the work described here involves compatibilization with
common, commodity polymers as matrices. The composite
gels discussed here show that the oligomer functionalized
photoactive molecules in the polymer based gels retain
their optical (aggregation) behavior and these could be
eventually candidates for uidic photoactive applications.
With the gels also, we used common polymers: polystyrene with a Tg of 100 C and PDMS with a Tg of 100 C.
Acknowledgements
Financial support from the Natural Sciences and Engineering Research Council of Canada is gratefully acknowledged. We thank Dr. M.R. Islam of our group for the OM
shown in Fig. 1(c)(e).

[11]

[12]

[13]
[14]

[15]

[16]

[17]

[18]

[19]
[20]

[21]

[22]
[23]

[24]

Appendix A. Supplementary material

Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.eurpolymj.2014.11.022.
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Dr. Elianne Dahan graduated from Carleton

University with a Doctorate of Philosophy in
Chemistry in January 2014. Her doctoral
research was on The Gelation and Morphology
of RodCoil and CoilRodCoil Molecules
Based on Perylene Diimide. E.D. was a recipient of the Ontario Government Scholarship
for Science and Technology in 2011 as well as
well as a recipient of the Queen Elizabeth II
Graduate Scholarship in 2012.

Dr. Sundararajan (Sundar) graduated from

the University of Madras in 1969. He spent
post-doctoral tenures with Professor Paul
Flory at Stanford University and with
Professor Bob Marchessault at University of
Montreal. Sundar was then employed at Xerox
Research Centre of Canada in Mississauga,
Ontario for 25 years, as a member of research
staff, Manager of Materials Characterization
and as Principal Scientist. His work at Xerox
was focused on morphology of photoreceptors, simulation of polymer conformations
and chain-folding. He became a professor at the Department of Chemistry, Carleton University in Ottawa, Canada in 2000 as the NSERC-Xerox
Industrial Research Chair. Sundars current research is on morphology of
polymer composites, self-assembly, organo- and polymer gelation. He is a
Fellow of the Chemical Institute of Canada and the winner of the
Macromolecular Science and Engineering Award of the Chemical Institute
of Canada and the Materials Chemistry Award of the Canadian Materials
Society. He has published over 150 papers and holds 10 patents.