Structural complexity induced by topology change in hybrids consisting of hexa-: Peri -hexabenzocoronene and polyhedral oligomeric silsesquioxane

Article abstract of DOI:10.1039/c7cc04897a

Organic-inorganic hybrids with hexa-peri-hexabenzocoronene (HBC) and polyhedral oligomeric silsesquioxane (POSS) were designed and synthesized. The increase of the POSS content (or a change in topology) results in more complex self-assembled structures. This work provides a new approach for the design and synthesis of materials with sub-10 nm sizes.

Full text of DOI:10.1039/c7cc04897a

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Structural Complexity Induced by Topology Change in Hybrids
Consisting of Hexa‐peri‐hexabenzocoronene and Polyhedral
Oligomeric Silsesquioxane
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Meng‐Yao Zhanga, Sheng Zhoua, Hongbing Pan a, Jing Ping a, Wei
Zhang a, Xing‐He Fana, and Zhihao Shena,*
www.rsc.org/
moieties which are unsuitable for etching. Therefore, new
POSS‐based shape amphiphiles need to be prepared to
generate various hierarchical structures for nanotemplates.
The phase behaviors of shape amphiphiles are influenced by
many factors, such as linkers between different segments and
the content of each segment. When different linkers were
used to connect Zinc porphyrin and [60] fullerene (C60),
nanotubes with different diameters were obtained in
solution.16 Triphenylene (Tp)‐POSS dyad with one Tp and one
POSS covalently connected was found to form a lamellar
structure; however, when the number of Tp was increased to 8,
the shape amphiphiles formed columnar structures.12,13 Hexa‐
peri‐hexabenzocoronene (HBC) is a planar molecule with a
large π‐conjugated core, and it can self‐assemble into highly
ordered columnar structures in bulk.17‐20 In our previous work,
the effect of the length of the linker on the self‐assembling
behaviors of HBC‐POSS dyads was investigated.21 At ambient
temperature, only the linker with three methylene units was
suitable for the formation of highly ordered structures. And at
higher temperatures, apart from a long linker with 20
methylene units, the other three dyads all formed hexagonal
columnar (Colh) structures. Thus, other factors need to be
introduced to tune the phase behaviors of shape amphiphiles
containing HBC and POSS in order to generate hierarchical
and/or more complex structures with sizes below 10 nm.
Organic‐inorganic hybrids with hexa‐peri‐hexabenzocoronene
(HBC) and polyhedral oligomeric silsesquioxane (POSS) were
designed and synthesized. The increase of the POSS content (or
change in topology) results in more complex self‐assembled
structures. This work provides a new approach for the design and
synthesis of materials with sub‐10 nm sizes.
Hierarchical structures have a wide variety of applications in
the fields of organic electronics, solid‐state electrolytes, and
nanopatterning.1, 2 Thus, many efforts have been made to
search an effective way to obtaining hierarchical structures.
Self‐assembly is one of the most used methods to obtain
ordered structures.3 Recently, shape amphiphiles, composed
of nano‐sized segments with distinct shapes and competitive
interactions, are found to be able to self‐assemble into various
complex hierarchical structures in bulk.4,5 Compared to
polymers, the molecular weights of shape amphiphiles are
accurate without polydispersity. As a result, sharp interfaces
between different domains can be obtained, which is
important for nanopatterning. Because of the relative small
molecular weights, shape amphiphiles have feature sizes
around 10 nm or smaller, which length scale is important for
microelectronics, and fast self‐assembly dynamics which is
beneficial for the formation of long‐range ordered structures
with a low defect density.6,7 And shape amphiphiles generate
Herein, the POSS content and thus the architecture or
topology of the HBC‐POSS hybrids was changed to obtain
various structures from these hybrids. The chemical structures
unconventional
structures.8
Polyhedral
oligomeric
silsesquioxane (POSS) is composed of a rigid inorganic core and
organic peripheries.9,10 The inorganic silicon‐oxygen backbones
of POSS can increase etching contrast of the materials. Thus,
POSS‐containing materials have been utilized to prepare
nanotemplates.11 POSS‐based shape amphiphiles often form
lamellar or columnar structures.12‐15 Unconventional
structures8 are formed by molecules consisting of all POSS
of HBC‐nPOSS‐COO (nE, n = 1, 2, 6) are illustrated in Chart 1.
The molecular design is based on the following considerations.
First, the substituents at the periphery of HBC were changed
from the linear –C12H25 chains in our previous work to the
branched chains with a total of 16 carbon atoms to balance
the interactions of HBC‐HBC, POSS‐POSS, and HBC‐POSS for
better packing. Second, a relatively long linker was chosen to
ensure better microphase separation between HBC and POSS
units. Last but not the least, the linker of 6E was a bit different
from that of 1E and 2E due to synthetic considerations. Herein,
a. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer
Chemistry and Physics of Ministry of Education, Center for Soft Matter Science
and Engineering, College of Chemistry and Molecular Engineering, Peking
University, Beijing 100871, China. E‐mail: zshen@pku.edu.cn
Electronic Supplementary Information (ESI) available: Synthetic route of
precursors, thermogravimetric analysis (TGA) curves of nE, 2D WAXD and TEM
the self‐assembling behaviors of
nE were studied by using
various techniques. These hybrids can generate hierarchical
n
E
structures all with feature sizes below 10 nm, with increasing
structural complexity when n increases.
results of 2E, and crystallographic data of 2E. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
C6H13
i-C4H9
C6H13
C8H17
View Article Online
DOI: 10.1039/C7CC04897A
Si
O
O
O
C8H17
Si
O
O
i-C4H9
Si
O
Si
O
O
Si
i-C4H9
i-C4H9
O
O
O
O
C8H17
Si
Si
i-C4H9
O
O
C6H13
i-C4H9
C8H17
C6H13
C8H17
C6H13
1: HBC-1POSS-COO (1E)
i-C4H9
Si
O
Si
O
O
O
O
i-C4H9
Si
Si
O
O
O
Si
i-C4H9
i-C4H9
O
O
O
O
O
Si
Si
O
C6H13
C8H17
i-C4H9
i-C4H9
i-C4H9
C8H17
Si
O
O
O
Si
C6H13
O
O
Si
O
Si
O
O
i-C4H9
i-C4H9
O
O
O
Si
O
Si
Figure 2. DSC thermograms of nE (n = 1, 2, 6).
i-C4H9
O
Si
O
Si
C8H17
C6H13
i-C4H9
C8H17
i-C4H9
C6H13
2: HBC-2POSS-COO (2E)
Polarized light microscopy (PLM) (Figure S2 in ESI) was also used to
examine the phase behaviors of nE (n = 2, 6), and the results are
consistent with the DSC data.
R
R
i-C4H9
Si
O
i-C4H9
Si
O
R =
O
O
R
O
O
i-C4H9
i-C4H9
Si
O
Si
O
Si
O
O
i-C H9
O4
O
To determine their phase behaviors, temperature‐dependent
small‐angle X‐ray scattering (SAXS) experiments were performed.
For 1E (Figure S3a in ESI), there are three diffraction peaks at q =
0.78, 2.78, and 5.89 nm1 in the low‐angle region of the SAXS profile.
However, the q values of the three peaks do not have a simple,
proportional relationship. The first peak corresponds to a d‐spacing
(d1) of 8.05 nm, which is close to two times of the molecular size of
4.5 nm simulated by ChemOffice 3D (Figure S3b in ESI). The d‐
spacings of the second (d2) and third (d3) peaks can be attributed to
the lateral spacing between two neighboring HBC units and the
distance between two POSS moieties, respectively. Thus, the
structure of 1E at ambient temperature is a poorly ordered packing
with small domains, as shown in Figure S3c in ESI.
O
Si
i-C4H9
R
O
Si
R
R
3: HBC-6POSS-COO (6E)
Chart 1. Chemical Structures of
nE (n = 1, 2, 6).
The synthesis of (n = 1, 2, 6) is shown in Scheme S4 in
n
E
Electronic Supplementary Information (ESI). The functional
HBC and POSS derivatives were synthesized separately and
then covalently connected through Steglich esterification22 or
Sonogashira reaction.23,24 For 6E, a different linker was used
because of the quite low yield of the esterification with several
acid groups reacting simultaneously. All the final compounds
have been fully characterized by 1H NMR, 13C NMR, elemental
analysis, and matrix‐assisted laser desorption/ ionization time
of flight (MALDI‐TOF) mass spectrometry to unambiguously
confirm their chemical structures. The most convincing
evidence was provided by the MALDI‐TOF mass spectrum
(Figure 1) in which only one strong peak matching the
proposed structure of the target molecule was observed. For
example, the observed peak at m/z 2685.6 of [1E]+ agrees well
with the calculated monoisotopic molecular mass (2685.8 Da) .
The bulk phase transitions in samples nE (n = 1, 2, 6) were
studied by the differential scanning calorimetry (DSC) technique
(Figure 2), and the results are summarized in Table S1 in ESI.
Because of the unbalanced interactions among HBC and POSS
moieties, 1E only exhibits a structure lack of high ordering. More
POSS moieties are needed to balance the interactions to generate
highly ordered structures. Thus, 2E was designed and synthesized.
Figure S4 in ESI shows the SAXS and temperature‐dependent wide‐
o
angle X‐ray diffraction (WAXD) profiles of 2E. At 130 C, there are
only broad halos in the WAXD profile, indicating the isotropic state.
When temperature decreased, there are multiple peaks in both
low‐angle and high‐angle regions at 90 oC and 30 oC. The
characteristic peaks of the crystalline rhombohedral (KR) structure
1
of POSS at q = 5.90, 7.82, and 8.55 nm are present in the WAXD
profile (Figure S4b in ESI).25 Thus, with the increase in the content
of POSS and the V‐shaped architecture of 2E in which the two POSS
moieties can stay at the same side of HBC, more POSS units
aggregate together, and the structure of POSS moieties becomes
more ordered. And the synergetic interactions among HBC and
POSS also result in two ordered phases at different temperatures.
o
o
Comparing the WAXD profile quenched at 90 C with that at 30 C
during the cooling process, there is an additional peak with q =
1
o
13.65 nm appearing at the WAXD profile at 30 C, which can be
indexed as the (002) diffraction. This peak corresponds to a d‐
spacing value of 0.46 nm, indicating the herringbone packing of HBC
moieties with the aromatic cores stacked in a tilted fashion at an
o
angle of 40 along the c axis. Thus, the two exothermic peaks in
DSC can be referred to the transition from the isotropic state to the
2D monoclinic structure and that from a 2D monoclinic structure to
a 3D monoclinic one. The parameters of the 3D monoclinic unit cell
can be determined as a = 8.33 nm, b = 2.48 nm, c = 0.92 nm, and γ =
o
89.8 . The detailed data are summarized in Table S2 in ESI. Two‐
dimensional (2D) WAXD and transmission electron microscopy
Figure 1. MALDI‐TOF mass spectra of nE (n = 1, 2, 6).
2 | J. Name., 2012, 00, 1‐3
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(TEM) results (Figure S5 in ESI) are consistent with the determined
monoclinic unit cell. For the 2D monoclinic structure, it is
disordered along the c direction, and other parameters are the
same as those of the 3D monoclinic one.
View Article Online
DOI: 10.1039/C7CC04897A
Interestingly, 6E, which is the most symmetric hybrid in this series,
exhibits more complex structures. Figure 3 shows the temperature‐
dependent SAXS profiles and WAXD profile at 30 oC of 6E. Because
the two endothermic peaks during heating are quite close, data
obtained during cooling were used to determine phase structures.
As shown in Figure 3a, there are two changes in the SAXS profiles
during the cooling process, which is consistent with the two
exothermic processes in the first‐cooling DSC curve. At ambient
temperature, four diffraction peaks are observed at q = 1.31, 2.25,
1
2.60, and 3.44 nm in the SAXS profile (Figure 3a), with a ratio of
1:31/2:2:71/2. These peaks can be assigned as the (10), (11), (20), and
(21), respectively, diffractions of a 2D hexagonal columnar (Colh)
structure with a = 5.53 nm. In the high‐angle region, there are also
several peaks (indicated by the black arrows in Figure 3b) at q =
1
5.81, 7.02, 7.77, 8.65, 9.71, and 13.52 nm . These peaks can be
indexed as the (101), (002), (110), (012), (201), and (113),
respectively, diffractions of a rhombohedral POSS structure (KR)
with a = b = 1.61 nm, c = 1.71 nm, and γ = 120 o, which are the same
as those of the octaisobutyl‐POSS reported in the literature.26 Other
peaks in Figure 3b with a q ratio of 31/2:2:71/2:3:121/2 belong to the
Colh structure. Hence, a hierarchically ordered structure is formed
with a nanometer‐scale supramolecular Colh liquid crystalline (LC)
phase of the hybrid and ~1 nm‐scale KR crystal of POSS coexisting
for 6E at ambient temperature. Two‐dimensional WAXD patterns
(Figure S6a, b in ESI) verify the above determination of the structure.
And in the TEM images (Figure S6d, e in ESI), columns parallel to the
substrate with a spacing of 5.6 nm were observed, which is
consistent with the SAXS results.
Figure 4. Synchrotron‐radiation SAXS profile at 215 oC of 6E (a), 2D
WAXD patterns of a sheared sample of 6E at 200 C with the X‐ray
beam along the Z direction (b), and the shearing geometry (c).
o
When temperature is increased to above 200 oC, there is a
remarkable change in the SAXS profile (Figure 3a). The scattering
vector ratio of the peaks belonging to the supramolecular structure
changes from 1:31/2:2:71/2 to 1:21/2:31/2:41/2:51/2, indicating the
development of a new body‐centered cubic (BCC) phase (space

group Im3m) with a = 6.24 nm. And the peaks from the KR structure
of the POSS moieties disappear. The SAXS profile with higher
resolution in Figure 4a confirms the BCC phase. As shown in the 2D
WAXD pattern, there are six reflections from the BCC phase (Figure
4b). The experimental value of the density at ambient temperature
is 1.09 g/cm3. According to the cell parameters and the density of
the BCC phase, one sphere contains 11 molecules, indicating that
these 11 molecules aggregate to form a sphere. The aggregation
should be facilitated by the ‐ stacking of the HBC discs.
At 150 oC during cooling from higher temperatures, the
supramolecular structure changes from BCC to Colh, with the POSS
moieties still remaining in the amorphous state indicated by the
broad halo at q = 6 nm1 shown in Figure 3a. When temperature is
further decreased, the peaks from the supramolecular structure
remain unchanged whereas sharp diffractions from the POSS
moieties develop. Hence, 6E also forms a hierarchical structure with
a Colh supramolecular LC phase of the whole molecule and the KR
crystalline phase of POSS coexisting at ambient temperature. When
temperature increases, the KR structure melts first and the Colh
phase remains. When temperature continues increasing, the π‐π
interaction is weakened. Consequently, the Colh‐to‐BCC transition
occurs for energy minimization.26
As mentioned above, the structure of 1E at ambient
temperature is a poorly ordered packing with small domains, as
shown in Figure S3 in ESI. For the molecular arrangements of 2E at
ambient temperature, with the consideration of the value of a and
the size of one molecule, there should be two molecules along the a
direction. Hence, the molecule adopts a head‐to‐head and tail‐to‐
tail arrangement with HBC moieties stacked in a tilted fashion at an
angle of 40o along the c axis. Between two HBC layers, POSS
Figure 3. Temperature‐dependent SAXS profiles (a) and
synchrotron‐radiation WAXD profile at 30 oC (b) of 6E.
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moieties form ABCA four layers. Two POSS units of the same 2E to the wide variety of functional nanoparticles. Such a HBC‐POSS
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molecule are located in different layers. When temperature system may be useful as templates for sub‐1D0OnI:m10p.1a0t3t9e/rCn7inCgC.04897A
increases, the packing of HBC moieties becomes disordered. With
This research was supported by the National Natural Science
the increase in the content of POSS, the architecture of 6E changes Foundation of China (Grant 21674004).
from the asymmetric V‐shape to a six‐fold symmetric shape, leading
to a change in the molecular arrangement of 6E. To investigate
molecular arrangement of 6E, the electron density map (Figure S7
Notes and references
in ESI) was reconstructed by using the (hk0) data in the SAXS profile
1
T. Aida, E. W. Meijer and S. I. Stupp, Science, 2012, 335, 813‐
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at 150 oC. The red zones with the highest electron density should be
the HBC and POSS moieties. Considering the chemical structure of
6E, the circular red zone should be the HBC moieties. Hence, the
HBC moieties stay in the centre of the column, and the POSS
moieties are at the periphery. As the peaks originating from the
Colh phase remain unchanged in the SAXS profile when temperature
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4
o
is decreased to 30 C, the columnar arrangement should be the
same as that at 150 oC. And each column contains one 6E molecule
in the ab plane. Each molecule in three neighboring columns
contributes one POSS moiety to construct the crystalline structure
of POSS with ABCA four layers. The schematic drawing of the phase
structures of nE (n = 2, 6) is shown in Figure 5.
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In conclusion, nE (n = 1, 2, 6) was prepared by separately
synthesizing HBC and POSS moieties and then covalently connecting
them. The content of the POSS moiety (or change in topology) was
changed to effectively tune the self‐assembling behaviour of nE.
With increasing content of the POSS moieties, the transition
temperature increases. And the structures at ambient temperature
change from low ordered for 1E to long‐range ordered for 2E and
6E. 2E forms a hierarchical structure with a supramolecular
monoclinic unit cell coexisting with the KR crystalline structure of
POSS moieties. 6E remains ordered during the whole experimental
temperature range and exhibits two order‐to‐order transitions: Colh
coexisting with KR of POSS moieties to Colh and Colh‐to‐BCC. The
complex BCC phase is seldom found in systems constructed by rigid
nanoparticles. Thus, except that 1E only forms a low ordered
structure, the other two samples form long‐range ordered
structures with sizes all below 10 nm. This may open a new avenue
for obtaining hierarchically ordered structures with molecular
precision and monodispersity on the sub‐10 nm length scale owing
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Figure 5. Schematic diagram of the self‐assembling behaviors of nE
(n = 2, 6).
4 | J. Name., 2012, 00, 1‐3
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Graphical Abstract for
Structural Complexity Induced by Topology Change in Hybrids Consisting of
Hexa-peri-hexabenzocoronene and Polyhedral Oligomeric Silsesquioxane
Meng-Yao Zhang, Sheng Zhou, Hongbing Pan, Jing Ping, Wei Zhang, Xing-He Fan and Zhihao
Shen*
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and
Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of
Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
O
rganic-inorganic hybrids with hexa-peri-hexabenzocoronene (HBC) and polyhedral oligomeric
silsesquioxane (POSS) were designed and synthesized. The increase of the content of POSS
moieties (or change in topology) results in more complex self-assembled structures. This work
provides a new approach for the design and synthesis of materials with sub-10 nm sizes.