Supramolecular Non-Helical One-Dimensional Channels and Microtubes Assembled from Enantiomers of Difluorenol

Article abstract of DOI:10.1002/anie.202012548

The design and assembly of photoelectro-active molecular channel structures is of great importance because of their advantages in charge mobility, photo-induced electron transfer, proton conduction, and exciton transport. Herein, we report the use of racemic 9,9′-diphenyl-[2,2′-bifluorene]-9,9′-diol (DPFOH) enantiomers to produce non-helical 1D channel structures. Although the individual molecule does not present any molecular symmetry, two pairs of racemic DPFOH enantiomers can form a C₂-symmetric closed loop via the stereoscopic herringbone assembly. Thanks to the special symmetry derived from the enantiomer pairs, the multiple supramolecular interactions, and the padding from solvent molecules, this conventionally unstable topological structure is achieved. The etching of solvent in 1D channels leads to the formation of microtubes, which exhibit a significant lithium-ion conductivity of 1.77×10^?4 S cm, indicating the potential research value of this novel 1D channel structure.

Full text of DOI:10.1002/anie.202012548

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Accepted Article
Title: Supramolecular Non-helical One-dimensional Channels and
Microtubes Assembled from Enantiomers of Difluorenol
Authors: Sha-Sha Wang, Yi-Ran Liu, Xiang Yu, Yang Zhou, Tao-Tao
Zhong, Yue-Tian Li, Ling-Hai Xie, and Wei Huang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202012548
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10.1002/anie.202012548
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COMMUNICATION
Supramolecular Non-helical One-dimensional Channels and
Microtubes Assembled from Enantiomers of Difluorenol
Sha-Sha Wang[a], Yi-Ran Liu[a], Xiang Yu[a], Yang Zhou[a], Tao-Tao Zhong[a], Yue-Tian Li[a], Ling-Hai
Xie*[a] [b] and Wei Huang*[a] [b]
[a]
Dr. S.-S. Wang, Y.-R. Liu, X. Yu, Y. Zhou, Y.-T. Li, T.-T. Zhong, Prof. L.-H. Xie and Prof. W. Huang
Centre for Molecular Systems and Organic Devices (CMSOD), Key Laboratory for Organic Electronics and Information Displays and Jiangsu Key
Laboratory for Biosensors, Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Institute of Advanced Materials (IAM), Nanjing
University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing 210023, China.
[b]
Prof. W. Huang and Prof. L.-H. Xie
Frontiers Science Center for Flexible Electronics (FSCFE), MIIT Key Laboratory of Flexible Electronics (KLoFE), Shaanxi Key Laboratory of Flexible
Electronics, Xi'an Key Laboratory of Flexible Electronics, Xi'an Key Laboratory of Biomedical Materials & Engineering, Xi'an Institute of Flexible Electronics,
Institute of Flexible Electronics (IFE), Northwestern Polytechnical University, Xi'an 710072, Shaanxi, China
Supporting information for this article is given via a link at the end of the document.
E-mail: Wei Huang: wei-huang@njtech.edu.cn; Ling-Hai Xie: iamlhxie@njupt.edu.cn; Sha-Sha Wang: iamsswang@njupt.edu.cn
ORCID: Wei Huang: 0000-0001-7004-6408; Ling-Hai Xie: 0000-0001-6294-5833; Sha-Sha Wang: 0000-0002-8724-4627; Ling-Zhi Jin: 0000-0002-4036-4576
leads to a variety of different topologies covering triangular,
tetragonal and hexagonal patterns.[6] In addition, the building
Abstract: The design and assembly of photoelectro-active
blocks with asymmetric structures such as steroidal ureas and
molecular channel structures is of great importance because of their
bile acids can form channels through helical arrangement with
supramolecular chirality.[7] Despite these strategies, the design
special advantages in charge mobility, photo-induced electron
transfer, proton conduction and exciton transport. Besides
macrocycle stacking and knot + linker connection, this work rarely
provides a fresh strategy for the exquisite design of 1D channel
based on a pair of mirror isomers. Racemic 9,9'-diphenyl-[2,2'-
bifluorene]-9,9'-diol (DPFOH) enantiomers were proved to be utilized
as newfashioned building modules for the non-helical 1D channel
structures. Although the individual molecule doesn’t present any
molecular symmetry, two pairs of racemic DPFOH enantiomers can
form a C2-symmetric closed loop via the stereoscopic herringbone
assembly. Thanks to the special symmetry derived from the
enantiomer pairs, the multiple supramolecular interactions and the
padding from solvent molecules, this conventionally unstable
topological structure is achieved. The self-similar relationship of
tubular structures spanning from molecular level to microscale level
was explained. Finally, the lithium-ion transport performance was
demonstrated, showing a significant ion conductivity of 1.77×10-4
S/cm, indicating the potential research value of this novel 1D
channel structure.
of 1D channel is still an intriguing problem which calls for fresh
organic modules and assembly modes to enlarge the material
library. On the other hand, due to the geometry retention of
building units, the prediction of framework motifs is feasible at
the molecular level. But the further understanding of the
relationship between 1D channel structures and their crystal
morphologies in micro/nanoscale has been rarely reported.
Herein, we exhibit an unprecedented supramolecular 1D non-
helical channel structure based on racemic 9,9'-diphenyl-[2,2'-
bifluorene]-9,9'-diol (DPFOH) enantiomers. Although the
individual molecule doesn’t present any molecular symmetry,
two pairs of racemic DPFOH enantiomers can form a C2-
symmetric closed loop via the stereoscopic herringbone
assembly. Thanks to the special symmetry derived from the
enantiomer pairs, the multiple supramolecular interactions (C-
H…π, π…π and H-bonding forces) and the padding from
solvent molecules, this conventionally unstable topological
structure is achieved. The etching of solvent in 1D channels
leads to the formation of microtubes. Finally, the lithium-ion
transport performance was demonstrated, showing a significant
ion conductivity of 1.77×10-4 S/cm.
Organic frameworks with one-dimensional (1D) channel/column
structures have attracted considerable research interest
because of their special multi-functionalities in charge mobility,
photo-induced electron transfer, proton conduction and exciton
transport.[1] Furthermore, channel walls modified with active sites
allow diversified applications, including catalysis, pollutant
adsorption and molecular recognition.[2] The organization of 1D
channel in organic networks can be deemed as the aligned
packing of meshed 2D layers without interpenetration or
misregistration, as illustrated by many examples in covalent
organic frameworks (COFs) and supramolecular organic
frameworks (SOFs) involving hydrogen-bonded organic
frameworks (HOFs).[3] As a result, the design and construction of
channel structures is closely associated with the self-assembly
modes based on both the backbone architectures and the
bonding forces. Apart from the 1D face-to-face stacking of
macrocycle molecules, the most common strategy is utilizing
multi-armed monomers with the functional joint to provide
directional covalent or non-covalent interactions for the
sequential extension of reticular systems.[4] For example,
diaminotriazine, carboxylic acid, amide, benzimidazolone,
imidazole, pyridine and such organic groups with abundant H-
bonding interaction sites were considered for the terminal design
of assembly units.[5] The permutation and combination of the
units with different levels of symmetry (C2, C3, C4, C6 and Td)
Figure 1. Molecular structures of (R, R)-DPFOH and (S, S)-DPFOH. (a)
Chemical molecular structures of (R, R)-DPFOH and (S, S)-DPFOH. (b)
Crystal molecular structures of ((R, R)-DPFOH) and ((S, S)-DPFOH) mirroring
each other.
DPFOH is a wide-bandgap semiconductor material which could
be synthesized through a Suzuki coupling reaction as stated in
Supporting Information (SI, Scheme S1). With the thin-layer
chromatography (TLC) experiment in Figure S1, we found that
DPFOH is composed of two kinds of diastereomers: raceme
(rac-DPFOH) and mesomer (meso-DPFOH), and the rac-
1
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DPFOH were purified as characterized by 1H NMR in Figure S2.
It is well known that the rac-DPFOH include a pair of
enantiomers,[8] (R, R)- and (S, S)-DPFOH, and their chemical
structures are shown in Figure 1a. Colorless rod-like single
crystals of rac-DPFOH were obtained by slow solvent diffusion
of ethanol (EtOH) into chloroform (CHCl3) solution. Through
single-crystal X-ray diffraction(XRD), the crystal structure was
disclosed as a tetragonal space group I-4 with eight molecules in
a unit cell (Table S1), and (R, R)- and (S, S)-DPFOH
enantiomers show a 1:1 ratio in it. The crystal molecular
structures of (R, R)- and (S, S)-DPFOH are exhibited in Figure
1b. The individual molecule doesn’t present any axisymmetric or
centrosymmetric properties, instead there is a strict mirror
symmetry between a pair of (R, R)- and (S, S)-DPFOH
molecules. Both of them include a C-C connected fluorenyl
dimer acting as the coaxial rod-like backbone with a syn-
conformation where a slight twist occurs between two fluorene
planes (the corresponding dihedral angle is 21.86°). Two
benzene rings lie on the opposite side of the fluorene backbone
with large dihedral angles of 82.09° and 85.93°, and two
hydroxyls locate at the other side of the backbone relative to the
benzene rings. To distinguish the mirror isomers, (R, R)-DPFOH
is marked in light blue and (S, S)-DPFOH is marked in pink, and
benzene ring of (R, R)-DPFOH links with the dark blue benzene
ring of another (S, S)-DPFOH by the same C-H…π interaction
and in this way a closed single pore is formed. The bonding
forces between the pores are still C-H…π interactions as shown
in Figure 2c (see Figure S3 for details). In addition, some EtOH
molecules decorated inside the channels with hydrogen bonds
stabilize the pore structure to some extent (see Figure S4 for
details). The 1D tubular assembly is displayed in the left part of
Figure 2d with a nonplanar zigzag-shaped orifice, which is
undoubtedly distinct from the traditional bicontinuous
arrangement of the collection of right- and left-handed helices.[9]
The molecules in every layer parallel to each other and align
precisely along c-axis without any misalignment between layers.
The interlayer supramolecular forces involve C-H…π, π-π
interactions and hydrogen bonds (Figure S5). The
corresponding schematic representation in the right part of
Figure 2d more clearly demonstrates the 1D cylindrical channel
features through this special stereoscopic herringbone packing
mode. It is worth noting that in our crystalline network the single
building block is asymmetric, indicating the realizability of
asymmetric racemic molecules for the building of in-plane
reticular architectures. The theoretical Connolly surface area of
rac-DPFOH crystals was calculated using Materials Studio with
the benzene rings are marked in dark blue or yellow respectively, a 1.82 Å probe radius for N2, which is determined to be 649.71
in order to explain their stacking manner in the next section.
m2/g, comparable to the previously reported organic
frameworks.[10]
Figure 2. Crystal structure analysis of rac-DPFOH crystal (light blue: (R, R)-
DPFOH, pink: (S, S)-DPFOH, red: hydroxyl). (a) The top view of a single layer
from c-axis exhibits the pore structures. (b) The side view of a single pore
shows the stereoscopic herringbone arrangement and the connecting
interactions from b-axis. (c) The relative position and interactions of two
adjacent pores viewed from c-axis. (d) The aligned packing of rac-DPFOH and
the corresponding schematic diagram (four different colors stand for four
different layers) along [001] direction across four layers represent the 1D
channel structure.
Figure 3. The morphologies and crystallographic structures of rac-DPFOH
microtubes. (a) SEM, (b) TEM images of the microtubes. Inset in (a): the SEM
image of
a single microtube. Inset in (b): the SAED pattern of the
corresponding microtubes and the electron beam direction is [110]. (c) The
schematic diagram of the microtube with indexed crystal faces and the
molecular arrangements of (1 0) and (001) crystal faces.
The crystalline structures of rac-DPFOH are illustrated in Figure
2 via different viewpoints to make the organic framework clear.
Viewed from c-axis, two kinds of pores with internal diameters of
9.6 Å and 3.8 Å can be observed in a single layer (Figure 2a).
Unlike the knot + linker strategy in which one branched knot
molecule may contribute to the construction of several pores,
here two pairs of enantiomer molecules form a relatively closed
pore structure (9.6 Å) without extended terminals. Furthermore,
each pore is contacted by four neighboring ones with a small
misalignment, generating a smaller pore (3.8 Å) surrounded by
four larger pores. To figure out the construction feature of this
pore structure, a side view of the larger pore in Figure 2b reveals
an unusual stereoscopic herringbone assembly. Four linear (R,
R)- and (S, S)-DPFOH molecules are standing obliquely on the
ab-plane and connected with each other head to tail along a
circular route. Specifically, the dark blue benzene ring of (R, R)-
DPFOH interacts with the yellow benzene ring of (S, S)-DPFOH
through a C-H…π interaction of 2.838 Å. Similarly, the yellow
The hollow channel structures are not only reflected at the
molecular level, the micro/nano morphologies of rac-DPFOH are
also investigated through a facile reprecipitation method, which
turn out to be tubular morphologies as well. The morphology and
structure of the rac-DPFOH microcrystals are shown in Figure
3a and 3b by SEM (scanning electron microscopy) and TEM
(transmission electron microscopy) with high morphological
purity. The microtubes have smooth surfaces and varied size,
with the average length is about 82.4 ± 24.8 μm, the edge
length 7.6 ± .5 μm, and the wall thickness 0.3 ± 0. μm. Some
microtubes are tend to aggregate into bundles and stand on the
substrate, so the hollow nature can be clearly observed by the
open-ended rectangular cross-sections (inset in Figure 3a),
which is also confirmed by the TEM image in Figure 3b. The
crystal structures of the microtubes were examined by powder
2
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X-ray diffraction (PXRD), and the patterns are consistent with
the rac-DPFOH single crystal, indicating the same crystalline
structures (Figure S6). The largest exposed crystal faces of the
environment have diffused into the channel (Figure 4f). On the
contrary, the distance-concentration curves of 0 ps and 100 ps
from (110) and (1 0)crystal faces remain unchanged (Figure S9),
reflecting there is no entry of EtOH molecules. This result is in
line with the conclusions we derived from experimental results. It
is hereby verified that the non-helical channels and self-similar
microtubes in our study are different from the traditional helical
tubes of amphiphiles with a twisted secondary structure.[15]
rac-DPFOH single crystal/microcrystal are assigned to
4
equivalent sets of {hh0} planes, inducing the strong diffraction
from {hh0} family different from the simulated pattern. The
selected-area electron diffraction (SAED) patterns (inset in
Figure 3b) of the microtubes can be indexed to (2 0) and (001)
faces, and the axial growth orientation is confirmed to be [001]
direction. Based on the above results, the schematic illustration
of a single microtube is revealed in Figure 3c with assigned tube
walls as {110} family, which is consistent with the Bravais Friedel
Donnay Harker (BFDH) simulation of rac-DPFOH crystal and the
attachment energies of {110} facets (Figure S7). By observing
the molecular accumulation of the microtube, it can be found
that the hollow direction of the microtube is consistent with the
axial of the 1D molecular channel.
Figure 5. Nyquist plot of rac-DPFOH microtubes at 25°C in a relative humidity
(RH) of ~65%.
The crystalline channels are idealized structures for ion and
molecule transport due to the excellent regularity and
designability. Several promising candidates have been explored
such as COFs,[16] metal-organic frameworks (MOFs)[17] and
HOFs[18] to deliver ions, especially protons. Compared with the
well-investigated proton conduction behavior, the lithium-ion
transport in supramolecular channel structures has been much
less explored. Here the lithium-ion conductivity of rac-DPFOH
microtubes was performed through electrochemical impedance
spectroscopy (EIS). 4.28 g LiClO4 was dissolved in 7.95 g
acetonitrile to prepare a solution with a mass fraction of 35%.
The microtubes was immersed in the solution for 24 hours, then
washed with acetonitrile and dried. The lithiated sample was
pressed into a thin pellet and sandwiched between two stainless
steel electrodes for conduction measurement. Nyquist plot of the
pellet exhibited a ion conductivity of 1.77×10-4 S/cm, which
could be comparable to the conventional solid polymer
electrolytes (～10-4 S/cm).[19] The stability of the samples has
been evaluated by cyclic EIS tests. The impedance spectra of
the lithiated sample keep almost the same within 5 cycles with
each time interval of 15 min, indicating the stable transport
behavior of the channels (Figure S10). The polar hydroxyl
groups are supposed to interact with lithium ions and promote
the dissociation of lithium salt.[20] Although the mechanism of ion
transfer is indeterminate, the hydrogen-bonding network within
the channels may act as the conducting pathway, learning from
the proton transport process.[21] In addition, based on the blue
light-emitting material DPFOH, the channel structure is
promising as a proof-of-concept platform for the further research
of ion-exciton interaction.
Figure 4. SEM images of rac-DPFOH samples after growing for (a) 10 min, (b)
30 min and (c) 12 h. (d) The proposed formation process of the microtubes. (e)
Kinetic simulation of molecular diffusion of EtOH molecules from (001) crystal
face occurred at 0 ps, 10 ps, 50 ps and 100 ps, respectively. (f) The
corresponding distance-concentration curve.
Previous works including cyclic peptide nanotubes[11] and
porphyrin hollow hexagonal nanoprisms[12] indicate that there is
a self-similar relationship between micro/nano tubular structures
and the corresponding 1D channel molecular packings, which
may concern the tube-forming mechanism. To reveal the growth
mechanism, the time-dependent evolution was performed as
shown in Figure 4a-c. The nanorods with an edge length of
about 270 nm can be obtained by growing for 10 min (Figure 4a).
Then the nanorods were growing with the edge length
increasing to about 500 nm, and the sharp open ends appeared
in some nanorods (Figure 4b). After that, the hollowing and the
growing processes were continued for 12 h, almost all of the
rods transformed into tubes with varying sizes (Figure 4c).
These phenomena indicate that the etching along with growing
simultaneously leads to the formation of the hollow structures.[13]
EtOH molecules are found in the molecular channels of rac-
DPFOH crystals, therefore it is supposed that the etching
process is caused by EtOH. The schematic diagram of the
etching process is shown in Figure 4d. EtOH molecules are
absorbed on the two ends of the rods with high attachment
energies (Figure S7) and gradually dissolve the (001) and (00 )
planes until the hollow tubes completed.[14] Additional, theoretical
calculations are introduced to describe the etching mechanism.
The kinetic process was simulated by the Forcite module of
Materials Studio software, which presents the diffusion of EtOH
molecules into 1D channels from (001) (Figure 4e), (110) and
(1 0) crystal faces (Figure S8). With longer diffusion time, more
and more EtOH molecules filled the channel from (001) face,
while few EtOH molecules can enter the crystal interior from
(110) and (1 0)crystal faces. Moreover, from the comparison of
the distance-concentration curves of 0 ps and 100 ps, it can be
seen that with time increasing, the concentration of EtOH
molecules on the right side of the curve declines, while on the
left rises, indicating that the EtOH molecules from the external
In summary, rac-DPFOH enantiomers were proved to be utilized
as newfashioned building modules for the non-helical 1D
channel structures. Besides macrocycle stacking and knot +
linker connection, this work provides a fresh strategy for the
design of 1D channel based on mirror isomers. The self-similar
relationship of tubular structures spanning from molecular level
to micron level was explained. Furthermore, the supramolecular
channel structures displayed high lithium ion conduct properties,
indicating the potential research value of this novel 1D channel
3
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Acknowledgements
[17]
[18]
This work was supported by the National Natural Science
Foundation of China (61604081), Natural Science Foundation of
Jiangsu Province, China (BM2012010), the Six Talent Peaks
Project of Jiangsu Province (XCL-CXTD-009), Project funded by
the Priority Academic Program Development of Jiangsu Higher
Education Institutions, PAPD (YX03002).
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Keywords: supramolecular interaction • non-helical channel •
enantiomers • self-similar structure • ion conductivity
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4
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Table-of-Contents
An unprecedented supramolecular non-helical channel structure based on
racemic 9,9'-diphenyl-[2,2'-bifluorene]-9,9'-diol enantiomers is achieved. Two
pairs of racemic enantiomers can form a C2-symmetric closed loop via the
stereoscopic herringbone assembly. The etching of solvent in 1D channels
leads to the formation of microtubes with a lithium-ion conductivity of 1.77×10-4
S/cm.
5
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