Stereospecific Epitaxial Growth of Bilayered Porous Molecular Networks

Article abstract of DOI:10.1021/jacs.0c00108

Stereocontrolled multilayer growth of supramolecular porous networks at the interface between graphite and a solution was investigated. For this study, we designed a chiral dehydrobenzo[12]annulene (DBA) building block bearing alkoxy chains substituted at the 2 position with hydroxy groups, which enable van der Waals stabilization in a layer and potential hydrogen-bonding interactions between the layers. Bias voltage-dependent scanning tunneling microscopy (STM) experiments revealed the diastereospecificity of the bilayer with respect to both the intrinsic chirality of the building blocks and the supramolecular chirality of the self-assembled networks. Top and bottom layers within the same crystalline domain were composed of the same enantiomers but displayed opposite supramolecular chiralities.

Full text of DOI:10.1021/jacs.0c00108

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Article
Stereospecific Epitaxial Growth of Bilayered Porous Molecular Networks
Yuan Fang, Benjamin D. Lindner, Iris Destoop, Takashi Tsuji, Zhenzhe Zhang, Rustam
Z. Khaliullin, Dmitrii F Perepichka, Kazukuni Tahara, Steven De Feyter, and Yoshito Tobe
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c00108 • Publication Date (Web): 18 Apr 2020
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Stereospecific Epitaxial Growth of Bilayered Porous Molecular Networks
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Yuan Fang,a,f Benjamin D. Lindner,b Iris Destoop,a Takashi Tsuji,b Zhenzhe Zhang,f Rustam Z.
Khaliullin,f Dmitrii F. Perepichka,f Kazukuni Tahara,b,c Steven De Feyter,a* and Yoshito
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Tobeb,d,e
*
aDepartment of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven,
Celestijnenlaan 200F, Leuven, B-3001, Belgium
bDivision of Frontier Materials Science, Graduate School of Engineering Science, Osaka
University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan
cDepartment of Applied Chemistry, School of Science and Technology, Meiji University,
1-1-1 Higashimita, Tama-ku, Kawasaki, 214-8571, Japan
dThe Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki,
Osaka, 567-0047, Japan
eDepartment of Applied Chemistry, National Chiao Tung University, 1001 Ta Hsueh Road,
Hsinchu, 30010, Taiwan
fDepartment of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Québec,
H3A 0B8, Canada
ABSTRACT
Stereo-controlled multilayer growth of supramolecular porous networks at the interface
between graphite and a solution was investigated. For this study, we designed a chiral
dehydrobenzo[12]annulene (DBA) building block bearing alkoxy chains substituted at the
2-position with hydroxy groups, which enable van der Waals stabilization in a layer and
potential hydrogen bonding interactions between the layers. Bias voltage-dependent scanning
tunneling microscopy (STM) experiments revealed the diastereoselectivity of the bilayer with
respect to both the intrinsic chirality of the building blocks and the supramolecular chirality of
the self-assembled networks. Top and bottom layers within the same crystalline domain were
composed of the same enantiomers but displayed opposite supramolecular chiralities.
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INTRODUCTION
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Self-assembled molecular networks (SAMNs) may spontaneously form on surfaces. In
contrast to self-assembled monolayers (SAMs) of alkanethiols chemisorbed on gold as an
example, the organization of the molecules in SAMNs only involves noncovalent interactions.
The molecules are physisorbed on the surface, very often lying flat on the surface and giving
rise to single-crystalline domains of a few atoms thick that can extend over several square
micrometers.1 Control over the structure and functionality of SAMNs on surfaces or at
liquid/solid interfaces has attracted broad interest in the context of nanoscience and
nanotechnology.2-3 Among the various types of two-dimensional (2D) architectures
constructed using molecular self-assembly, nanoporous networks are challenging structures
because of the necessity to surmount the inherent tendency of molecules to avoid the
formation of porous structures and assemble in a densely packed geometry. However, they are
highly attractive for applications in surface templating, nanopatterning, heterogeneous
catalysis and separations.4-6 Another challenge in this field is the controlled epitaxial growth
of SAMNs orthogonal to the substrate, a process with strong relevance to anchoring
three-dimensional (3D) metal-organic materials on surfaces (SURMOFs),7-9 electronics of
semiconducting molecules10 and crystal engineering.11 In particular, stereochemical
information about the first few molecular layers can provide insight into the evolution of
crystallization from 2D to 3D systems.12
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Among the various techniques used to probe the structure of ultrathin films, scanning
tunneling microscopy (STM) takes a unique position, as it provides submolecular resolution,
even at the interface between a solid substrate and a solution. Bilayers and multilayers were
studied using STM for planar π-conjugated molecules that self-assemble via π-π
interactions13-22 and for highly polarized molecules undergoing dipole-dipole interactions.22-23
Typically, the self-assembled second layer does not have a specific registry to the bottom
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layer. Specific point-to-point interlayer interactions are desirable to precisely control the
interlayer geometry.
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A few studies on the stereochemical relationship in both lateral (parallel to the surface)
and longitudinal directions (along the surface normal) of densely packed double layers grown
through van der Waals interactions have been performed using chiral molecules with a
twisted or helical backbone, such as rubrene,24 [5]helicene,25 and [7]helicene,26-27 under
ultrahigh vacuum (UHV) conditions. Because of their nonplanar structures, these molecules
are packed via van der Waals contacts in a point-to-point manner in both the lateral and
longitudinal directions. They form either a racemate or conglomerate double layer.28 More
specifically, the overlying second layer has opposite or the same handedness with respect to
the intrinsic chirality of the molecules themselves and supramolecular chirality of molecular
self-assembly. One study reports the nonlinear chiral amplification effect on bilayers of
near-racemic mixtures involving the biased adsorption and organization of the major
enantiomer at the liquid/solid interface.29
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For multilayered porous networks, although a few examples constructed through
longitudinal van der Waals or dipole interactions of intrinsically porous macrocyclic
molecules have been reported,30-35 the geometry of their nonbottom layers is not strictly
controlled or not determined. To the best of our knowledge, only two reports have described
the formation of porous double layer SAMNs using small nonmacrocyclic molecules, but
they do not address chirality.36-37
Here, we propose an approach to construct self-assembled porous multilayer films with
precise control over the interlayer geometry. For this purpose, we selected alkoxy-substituted
dehydrobenzo[12]annulene (DBA) derivatives because of their demonstrated ability to form
chiral porous honeycomb patterns via the interdigitation of alkoxy chains (Scheme 1)38-39 and
tunability of pore size by varying the alkoxy chain length.40 We reported the formation of
supramolecular networks of a well-defined handedness using chiral DBA (cDBA) molecules,
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such as cDBA-OC12(S) and cDBA-OC12(R) (Chart 1), with methyl-substituted stereogenic
centers, and their roles in inducing and inversing supramolecular chirality of networks of
achiral DBA molecules.41-43 Based on these results, we hypothesized that replacing the methyl
groups with hydrogen bonding groups would also lead to the formation of similar porous
chiral networks, and furthermore would enforce the formation of porous multilayers (Scheme
1), even in a stereo-controlled manner.
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Scheme 1. a) Typical supramolecular pore formed by alkylated DBA molecules. The type of
alkyl chain interdigitation determines the handedness of the supramolecular pores and the
supramolecular networks. b) Schematic of a self-assembled porous double layer structure;
chirality is ignored for simplicity. In the first step, the DBA molecules bearing polar hydroxy
groups (red squares) self-assemble into a honeycomb network on the surface via van der
Waals interactions between the alkoxy chains. The growth of the second layer is directed by
the van der Waals interactions between the two layers, possibly with the involvement of
longitudinal hydrogen bonding of the hydroxy groups.
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Therefore, we designed the chiral DBA derivatives cDBA-OC6-OH(S) and
cDBA-OC6-OH(R) with a hydroxy group at the 2-position of each hexyloxy chain (Chart 1).
We selected hexyloxy chains to promote the formation of the porous supramolecular structure
with relatively small pores of approximately 1.7 nm in diameter, as revealed previously for
DBA-OC6 (Scheme 1).44 Upon adsorption and self-assembly on the surface, the homochiral
cDBA-OC6-OH(S) and cDBA-OC6-OH(R) compounds are expected to form homochiral
porous patterns in either the clockwise (CW) or counter clockwise (CCW) direction through
(−) and (+) interdigitation modes of the alkoxy groups, respectively (Scheme 1 and Figure 1),
similar to the chiral DBAs with stereogenic methyl groups.41 More importantly, the hydroxy
substituents of cDBA-OC6-OHs should orient away from or towards the substrate in an
alternating manner, thereby promoting the formation of hydrogen bonds and a multilayer
structure. Therefore, the growth of the overlying layers may occur in a stereospecific manner
with respect to the first layer. The stereoselectivity at each step of self-assembly is
summarized in Scheme 2 to illustrate the stereochemical outcomes of the formation of the
anticipated multilayer structure.
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cDBA-OC12(S) R=
RO
OR
cDBA-OC12(R) R=
OH
OH
cDBA-OC6-OH(S) R=
RO
RO
OR
cDBA-OC6-OH(R) R=
DBA-OC6 R=
OR
Chart 1. Chemical structures of cDBA-OC12(S), cDBA-OC12(R), cDBA-OC6-OH(S),
cDBA-OC6-OH(R), and DBA-OC6.
Indeed, we revealed the formation of a bilayer of cDBA-OC6-OH(S) and
cDBA-OC6-OH(R) at the interface between graphite and a liquid using bias
voltage-dependent STM observations. The enantiomorphism of the bottom layer was identical
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to chiral DBAs bearing methyl groups on the chiral center [(Steps (1) and (2) in Scheme 2].
Most interestingly, the multilayer growth occurred in a diastereospecific manner between the
top and bottom layers with respect to both the intrinsic chirality of chiral DBAs, i.e., S on S vs.
S on R [Step (3)], and supramolecular chirality of the molecular network structures, i.e., CW
on CW vs. CCW on CW [Step (4)].
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Scheme 2. Schematic of the stereoselectivity in the formation of a self-assembled bilayer of
chiral DBA molecules. Blue and green triangles represent cDBA-OC6-OH(S) and
cDBA-OC6-OH(R), respectively. Chirality arising from the relationship between the
orientation of the molecules (or unit cell) with respect to the substrate symmetry axes is not
considered.45-47
Step
(1):
Supramolecular
enantiospecific
self-assembly
of
cDBA-OC6-OH(S) and cDBA-OC6-OH(R) forming clockwise (CW) and counter clockwise
(CCW) patterns, respectively (see also Figure 1d). Step (2): Stereoselectivity in a 1:1 mixture
of cDBA-OC6-OH(S) and cDBA-OC6-OH(R) forming a domain-separated “conglomerate”
consisting of CW and CCW domains; the corresponding “racemic compound” was not
observed. Step (3): Diastereospecificity in bilayer formation with respect to the intrinsic
chirality of cDBAs in the presence of excess cDBA-OC6-OH(S) or cDBA-OC6-OH(R). The
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formation of a bilayer with the same handedness, i.e., cDBA-OC6-OH(S) on top of
cDBA-OC6-OH(S) or cDBA-OC6-OH(R) on top of cDBA-OC6-OH(R), is favored. Step
(4): Diastereospecificity in bilayer formation with respect to the supramolecular chirality;
bilayers consisting of antipodal (CW/CCW) patterns of the honeycomb structure are favored
over patterns with the same handedness (CW/CW or CCW/CCW).
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RESULTS AND DISCUSSSION
Synthesis of cDBA-OC6-OH(S) and cDBA-OC6-OH(R)
The synthesis of the homochiral DBA derivatives cDBA-OC6-OH(S) and
cDBA-OC6-OH(R) is outlined in Scheme 3 for the S enantiomer. We prepared both
enantiomers of methoxymethyl (MOM) ethers of 1-bromo-2-hexanol through the selective
hydrolytic kinetic resolution of chiral epoxides using a chiral (salen)cobalt(III) catalyst,48
followed by regioselective ring opening of the chiral epoxide and MOM protection to insert
the hydroxy-containing chiral alkoxy groups into the DBA core. The chiral alkoxy group was
introduced to the iodoalkyne building block by coupling the bromide with 3,4-diiodocatechole,
followed by monoalkynylation. Copper-catalyzed cyclotrimerization of the iodoalkyne and
subsequent deprotection afforded cDBA-OC6-OH(S). Using the same procedure,
cDBA-OC6-OH(R) was prepared from the enantiomeric epoxide. The experimental details
are described in section 3 of the Supporting Information. The self-assembly of the analytically
pure chiral cDBA-OC6-OH(S) and cDBA-OC6-OH(R) was analyzed using STM at the
interface between highly oriented pyrolytic graphite (HOPG) and one main solvent at various
solute concentrations.
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Scheme 3. Outline of the synthesis of cDBA-OC6-OH(S). cDBA-OC6-OH(R) was prepared
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using the same procedure starting from the enantiomeric epoxide.
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Effects of the Solvent and Concentration on the Formation of a Monolayer and
Multilayers
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In the first step, we investigated the self-assembly of relatively low concentrations of
homochiral enantiomers and racemates of cDBA-OC6-OH(S) and cDBA-OC6-OH(R) at
liquid/solid interfaces. Regardless of the solvent [1,2,4-trichlorobenzene (TCB, Figure 1),
1-octanol (Figure S1a) or 1-phenyloctane (Figure S1b)],49 each enantiomer self-assembles
into the typical nanoporous honeycomb networks with opposite 2D chirality, similar to chiral
DBAs with stereogenic methyl groups, such as cDBA-OC12(S) and cDBA-OC12(R) (Chart
1).41 The DBA cores are lying flat on the substrate and the molecules are linked by van der
Waals interactions between the interdigitated alkoxy chains. Figure 1 displays STM images of
cDBA-OC6-OH(S) and cDBA-OC6-OH(R) at the TCB/HOPG interface, together with a
simplified molecular model. The unit cell parameters are a = b = 3.2 nm and the angle  = 60°.
These unit cell parameters are identical to the achiral analogue DBA-OC6 without hydroxy
groups.44 In most STM images, although the alkoxy chains are not clearly visible, the type of
interdigitation (+ or ‒) and the supramolecular chirality [clockwise (CW) or counter
clockwise (CCW)] can be determined from the lateral shift of adjacent DBA cores (Figure
1a-d). The overall handedness of the network can also be determined by the signs of the
rotation angles of a unit cell vector with respect to one of the symmetry axes of graphite
(Figures 1a-b and S2).
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Figure 1. STM images of cDBA-OC6-OH(S) a) and cDBA-OC6-OH(R) b) monolayers
formed at the TCB/HOPG interface (2.3 × 10−6 M). Black arrows indicate the graphite
reference axes. θ is the angle between a reference axis and one of the unit cell vectors. c and
d) Molecular models of (–) and (+) interdigitation patterns (c) and corresponding CW and
CCW nanowells (d) for cDBA-OC6-OH(S) (a) and cDBA-OC6-OH(R) (b), respectively.
Imaging conditions: (a) Iset = 0.2 nA and Vbias = −0.2 V and (b) Iset = 0.2 nA and Vbias = −0.5 V.
Consistent with the stereogenic methyl substitution on the alkyl chains of
cDBA-OC12(S) and cDBA-OC12(R),41-42 these compounds show enantiomorphous pattern
formation. The S enantiomer exclusively produces CW nanowells via (−) type interdigitation,
while the R enantiomer produces (+) interdigitated pairs, leading to the formation of CCW
nanowells (Figure 1). Because the supramolecular chirality of the network is the same as
cDBA-OC12(S) and cDBA-OC12(R),41-42 the roles of the hydroxy and methyl groups are
likely similar in biasing the alkoxy chain interdigitation type and establishing the chirality of
the nanowell domains [Step (1) of Scheme 2]. The observed selectivity is consistent with
molecular mechanics simulations under periodic boundary conditions (PBC) on a bilayered
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graphene whose geometry was fixed using COMPASS force field. For the R enantiomer, the
CCW nanowell formed by the (+) interdigitation type is 1.0 kcal mol−1 more stable than the
CW nanowell with the (−) interdigitation type (Figure S3).
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Once again, similar to their chiral analogues containing stereogenic methyl groups,41-42
when a racemic mixture of cDBA-OC6-OH(S) and cDBA-OC6-OH(R) was deposited at the
liquid/solid interface, enantiomorphous domains formed with equal surface coverage. As an
example, Figure 2 displays an STM image of racemic cDBA-OC6-OH at the TCB/HOPG
interface. Therefore, we conclude that a racemic conglomerate is formed at the liquid/solid
interface; both enantiomers assemble in different domains and are phase-separated [Step (2)
of Scheme 2].
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Figure 2. STM image showing the enantiomorphous domains of racemic chiral
cDBA-OC6-OH at the TCB/HOPG interface (C = 5.0 × 10−6 M, image size 50 × 50 nm2). In
the top left and bottom right panels, cDBA-OC6-OH(R) and cDBA-OC6-OH(S) domains are
colored green and red, respectively. The HOPG main symmetry axes are indicated by black
arrows. cDBA-OC6-OH(S) and cDBA-OC6-OH(R) domains are rotated by 24° and −24°
with respect to the surface reference directions (Figure S2). Imaging conditions: Iset = 0.2 nA
and Vbias = −0.2 V.
In contrast to any known DBAs, increasing the concentration of cDBA-OC6-OH leads to
noticeable changes in the structure and contrast of the STM images, except when 1-octanol is
used as the solvent (Figure S4). Carefully increasing the concentration from 2.3 × 10−6 M to
2.5 × 10−6 M in TCB49 produces two different types of contrast for the triangular DBA core
(Figure 3a and S5). In the higher magnification images (Figure 3b-d), the brighter cDBA
molecules are indicated by green dotted triangles. The cDBAs with the same relative position
as the brighter cDBA molecules are indicated by solid green triangles, while others are
indicated by solid black triangles. From these high-resolution data, the brighter triangle cores
of molecules numbered ①, ② and ③ appear to be rotated by 0°, 51° and 35° with respect to
other reference solid green triangles (Figure 3b-d and S5e-g). A line profile (Figure 3e and
S5a, c, and d) shows that the “high” DBA molecules are almost twice as high as the “low”
DBA molecules. Based on the height of these nonperiodic protrusions and their varying
orientations, we conclude that increasing the concentration led to the adsorption of single
molecules in the second layer.
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Figure 3. A high-resolution STM image of cDBA-OC6-OH(S) in TCB (C = 2.5 × 10−6 M)
reveals isolated molecules on top of the bottom layer. a) Large scale image (53 × 53 nm2).
b-c) Digital magnification of the image shown in (a). A full scale image of (d) is presented in
Figure S5b. b-d) Green dotted triangles indicate the orientation of the bright DBAs. The
cDBAs with the same relative position as the brighter cDBAs are indicated by solid green
triangles, while others are indicated by solid black triangles. e) Line profile across a “high”
DBA molecule, as indicated by the green line in panel (a). a-d) Imaging conditions: Iset = 0.2
nA and Vbias = −1.4 V.
A further increase in the concentration to 2.6 × 10−6 M increases the density of molecules
in the second layer (Figure 4), with the formation of on-top dimers. Interestingly, the relative
orientation of the triangles in this on-top dimer (Figure 4b and c) differs from the relative
orientation of adjacent molecules one layer below ((−) type interdigitation, Figure 4d). In the
former case, maximum overlap is observed between the two adjacent sides of neighboring
triangles, as opposed to the apparent shift of the molecules in the layer underneath.
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Figure 4. High-resolution STM image of cDBA-OC6-OH(S) in TCB revealing the initial
formation of second layer dimers. a) Large scale image (42 × 24 nm2; C = 2.6 × 10−6 M). b-d)
Digital magnification of the image shown in (a). The triangle cores of the second layer dimer
(b and c) appear to face each other as opposed to being shifted for monolayer dimers (d).
Imaging condition: Iset = 0.2 nA and Vbias = −1.4 V. e) Line profile across a second layer dimer,
as indicated by the green line in panel (a).
A further increase in the concentration (2.7 × 10−6 M) also leads to the formation of a
more extended second layer (Figure S6a). Actually, the second layer appears to be adsorbed
so strongly to the first layer that it is unable to easily be removed by rinses with the solvent
(Figure S6b). This finding differs from the SAMN formed from DBA-OC6, which does not
show any multilayer growth, even at a very high solution concentration of 1.2 × 10−2 M
(Figure S7). For related compounds carrying a methyl group on the chiral center,
cDBA-OC12(S) and cDBA-OC12(R), multilayer formation was never observed in the same
solvents.41
A partial double layer was also observed in a 1-phenyloctane solution for
cDBA-OC6-OH (Figure S8), while regardless of the concentration, only monolayer
formation was observed in 1-octanol (Figure S4). These results support but do not validate
our hypothesis that longitudinal hydrogen bonding promotes the growth of a second layer.
Bias Voltage Dependence of Monolayer versus Multilayers Imaging
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At a high concentration of the chiral DBA (> 2.9 × 10−6 M) in TCB, the image contrast
depends on the imaging conditions. For example, the two sequential images (taken 2 min
apart) in Figure 5a-b for cDBA-OC6-OH(R) (1 × 10−3 M) at the TCB/HOPG interface clearly
display the effect of the bias voltage. Figure 5a was recorded at the bias voltage (Vbias) of −0.5
V, whereas Figure 5b was recorded at Vbias of −1.2 V. The SAMN in Figure 5a contains
narrow domain boundaries, as indicated by white dashed lines, which are typically less than
one molecule wide. The STM image recorded at −1.2 V (Figure 5b) displays a remarkable
difference in contrast, showing some dark trenches that appear to coincide with the white
lines in Figure 5a to some extent. We tentatively interpret the difference in contrast at the
more negative sample bias to the visualization of the top layer of a multilayer structure.
Additional higher magnification images in Figure 5c with the respective height profiles
(Figure 5d) at large negative sample bias (Vbias = −1.1 V) further support the formation of
double layers. The line profile (Figure 5d) shows a significant difference in height between
the “low” and “high” DBA molecules, which supports the interpretation that the “high”
molecules are part of the top of a double layer or multilayer. Figure 5c reveals details of the
“dark trenches”: the multilayers do not readily grow at the domain boundaries.
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Figure 5. STM image of cDBA-OC6-OH(S) in TCB (1 × 10−3 M) showing the effect of the
bias voltage on the contrast of the multilayer structure. a and b) Sequential STM images (170
× 170 nm2) captured at a bias voltage of −0.5 V (panel (a) showing monolayer) and −1.2 V
(panel (b) showing double layer with dark trenches), respectively. White dashed lines in (a)
indicate domain borders. c) A higher magnification image (55 × 55 nm2) showing more
details of the dark trenches captured at sample bias voltage −1.1 V. d) Line profiles along the
green lines indicated in (c). e) In the middle of the image, the voltage increased from −1.2 V
(showing double layer) to −0.5 V (showing monolayer) (50 × 50 nm2) from top to bottom. In
the top half of the image, defects in the top layer (marked by green arrows in panel (e) and its
higher magnification image in panel (f)) allow us to visualize molecules in the lower layer,
which appear darker than the surrounding molecules. For all the images: Iset = 0.2 nA.
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By switching the bias voltage during scanning, the imaging mode is able to be switched
reversibly between multiple and single layers (Figure 5e). During scanning, the voltage was
increased from −1.2 V to −0.5 V. As a result, the top half of the image appears brighter than
the bottom half, consistent with the imaging of a multilayer at larger negative sample bias and
of a monolayer at smaller negative bias. Similar bias-voltage dependences of monolayer and
multilayers have been reported for some other systems.16, 20, 37, 50 Upon decreasing the absolute
value of the voltage, the tip-substrate distance decreases, and the STM tip likely penetrates
through the double layer to image the bottom layer (see the SI, including Figure S12, for more
information).
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Stereospecificity in Bilayer Formation
At a low concentration, a racemic solution of cDBA-OC6-OH (total concentrations of 5
× 10–6 M for TCB (Figure 2) and 2× 10–5 M for 1-phenyloctane (Figure S9)) self-assembles
into a domain-separated conglomerate consisting of domains of each enantiomer. Similarly, a
racemate at high concentration (> 1 × 10–4 M) also tends to form a domain-separated bilayer
(Figure S10). We investigated if bilayer formation is diastereospecific in terms of (i) the
intrinsic chirality of cDBAs in the first and second layers [Step (3) in Scheme 2] and (ii)
supramolecular chirality, i.e., CW/CCW patterns of the honeycomb structure, of the first and
second layers [Step (4) in Scheme 2].
First, we prepared a low concentration, equimolar solution of both enantiomers in TCB
and placed 20 μL of this solution in a liquid cell with the HOPG substrate. After network
formation was verified using STM, an excess amount of one of the enantiomers,
cDBA-OC6-OH(R) in the case of Figure 6, was added to the liquid cell. This sequential
addition protocol ensures that the domains of both enantiomers initially formed. STM
imaging at a small negative bias of –0.6 V clearly revealed the formation of separate CW and
CCW domains in the first layer (Figure 6a), similar to STM images of monolayers formed at a
low concentration (Figure 2). The domains in the upper and lower half of Figure 6a are
attributed to cDBA-OC6-OH(R) and cDBA-OC6-OH(S) domains, respectively, based on the
signs of the domain rotation angles with respect to one of the symmetry axes of graphite
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(Figures 2 and S11). By decreasing the bias voltage from –0.6 V to –1.2 V, a second layer is
observed exclusively on top of the CCW domain of cDBA-OC6-OH(R) (Figure 6b). Given
the excess amount of cDBA-OC6-OH(R) in solution, the exclusive observation of the double
layer on a CCW domain indicates that the top layer also consists of cDBA-OC6-OH(R).
Experiments in which an excess of cDBA-OC6-OH(S) was added produced similar results,
as shown in Figure S13. In the latter case, bilayer formation is only observed on CW domains.
When using a premixed solution of both enantiomers with an excess of one of the
enantiomers, a second layer is only observed on top of the domains formed by the major
enantiomer, consistent with the results obtained upon sequential addition (Figure S14).
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Figure 6. Enantioselective formation of a multilayer structure. The sequential addition of a
1:1 mixture of cDBA-OC6-OH(S) and cDBA-OC6-OH(R) (concentration of each
enantiomer = 3 × 10−4 M, 20 µL), followed by the addition of cDBA-OC6-OH(R) (1.2 × 10−3
M, 20 µL) in a liquid cell at the TCB/HOPG interface. (a - c) Images were captured after
excess cDBA-OC6-OH(R) was added. White dashed lines indicate domain boundaries. a and
b) Sequential images captured at the same location. a) Image of the bottom layer at –0.6 V.
The top domain is determined to be cDBA-OC6-OH(R) and the bottom domain is determined
to be cDBA-OC6-OH(S). For more details, see Figure S11. b) At –1.2 V, double layer
formation was observed only on top of the cDBA-OC6-OH(R) domain. c) The STM image
obtained by modulating the bias voltage during the scanning process. a-c) Image size 100 ×
100 nm2. Iset = 0.2 nA and Vbias are indicated in the image.
In addition to the domain-dependent layer growth, we are also able to monitor each layer
separately, depending on the chosen STM bias voltage. The contrast switch in the image
occurs instantaneously as the bias voltage is modulated. In Figure 6c, double layer formation
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is observed at –1.2 V, while the underlying bottom layer is revealed at –0.6 V. This approach
allows us to determine the handedness of the bottom layer and confirms that in the presence
of excess cDBA-OC6-OH(R), bilayer formation is only observed on top of the CCW bottom
layer domains. Figure S13 illustrates this principle for excess cDBA-OC6-OH(S). When a
racemic solution of cDBAs at relatively high concentration was used, domain-separated
bilayers consisting of homochiral domains of cDBA were observed, although we did not
determine their stereochemistry (Figure S10).
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No evidence is found that concentration-dependent aggregation in solution is involved in
the formation of these structures. In a CDCl3 solution, cDBAs exhibit a small
1
concentration-dependent H NMR chemical shift, suggesting weak aggregation (see
Supporting Information section 5). However, this shift is nearly identical in homochiral and
racemate solutions, refuting the idea of stereospecific association in solution. The
enantioselective formation of the double layer structure with respect to the intrinsic chirality
of cDBA is therefore concluded to be a specific phenomenon occurring at the interface
between the solid HOPG support and the solution on top.
Next, we investigated if bilayer formation is diastereospecific with respect to
supramolecular chirality of the first and second layers [Step (4), Scheme 2]. For example, for
the S enantiomer, the first layer adopts the CW honeycomb pattern through the (–) type
interdigitation of the alkoxy chains (Figure 1a). Depending on whether the second layer
adopts the antipodal CCW pattern or the same-handed CW pattern, the double layer will be
diastereomeric with respect to supramolecular chirality [Step (4) in Scheme 2]. Homochiral
solutions were used to probe the supramolecular chirality of the second layer while excluding
the possibility of interference from the DBA molecules with the opposite chirality. Figure 7a
shows an STM image of cDBA-OC6-OH(S) (1 × 10−3 M) at the TCB/HOPG interface. The
triangular features, which are highlighted by the black dotted lines, form a pattern with p6m
plane group symmetry, as opposed to the chiral p6 symmetry of the monolayer (Figure 7a,
inset).51 The appearance of this apparent achiral feature is potentially explained in terms of
offset of shifts between overlapping antipodal triangles, as shown in Figure 7b. This type of
staggered packing was observed for the crystal packing of other DBA derivatives (achiral), as
evidenced by single crystal structures.52-53 Accordingly, we deduce that the second layer
adopts an antipodal supramolecular chirality, i.e., CCW on CW and CW on CCW, for
cDBA-OC6-OH(S) and cDBA-OC6-OH(R), respectively.
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Figure 7. a) STM image of the self-assembly of a multilayered cDBA-OC6-OH(S) structure
(1 × 10−3 M) at the TCB/HOPG interface (20 × 20 nm2). The black dashed triangles indicate
the apparent orientations of the triangle DBA cores of the multilayer. Inset: Monolayer
self-assembly of cDBA-OC6-OH(S). Note the change in the plane group from chiral p6 to
achiral p6m for the monolayer (inset) and double layer (panel (a)), respectively. b) Proposed
multilayer growth model where the bottom layer and the second layer have opposite
interdigitation patterns. At the dimer level for cDBA-OC6-OH(S), the bottom layer (green)
adopts the (–) interdigitation pattern (see Figure 1), while the second layer (red) adopts the (+)
interdigitation pattern. At the supramolecular hexagonal nanowell level, the bottom layer
(green) exhibits the CW pattern (see Figure 1), while the second layer (red) displays the CCW
pattern. The red and green triangle cores are right on top of each other but rotated. The STM
contrast shows a superimposed image of two rotated DBA triangle cores in the first and
second layer, as outlined by the dotted triangles. Imaging conditions: Iset = 0.2 nA and Vbias
−1.4 V.
=
A series of molecular mechanics (MM) optimizations using COMPASS force field were
performed to obtain insights into the molecular structure of and intermolecular interactions in
different bilayers. Table S1 shows the lowest energy local minima we observed for bilayers
composed of cDBA-OC6-OH(R) and cDBA-OC6-OH(R)/cDBA-OC6-OH(S) (Figure S15).
When both layers have the same supramolecular chirality (e.g., CCW/CCW or Figure S15a),
their DBA cores are laterally shifted with respect to each other, and when the layers differ in
supramolecular chirality (e.g., CCW/CW or Figure S15c), their DBA cores are rotated with
respect to each other. This finding forms the basis for the assignment of chirality of the layers
in STM images of different bilayers (Figure S15). The MM optimizations also reveal that
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certain OH groups are capable of forming hydrogen bonds (OH···O distances ranging
between ca. 1.7 and 2.1 Å, Table S2), providing additional stabilization to bilayer structures.
The estimated energy values (Table S1) are not consistent with the experimental results. This
latter point is not surprising considering the conformational flexibility in these systems and
our neglect of the role of the solvent. In addition, kinetic factors may overrule thermodynamic
equilibrium. Indeed, the annealing of a solution of cDBA-OC6-OH(R) in TCB on HOPG at
80 °C for 10 min resulted in the formation of a new phase, the trimer phase (Figure S16).38
This result indicates the complexity of the system, where the multilayer is a metastable or a
kinetically trapped phase. A further detailed analysis of the stability of the multilayer vs other
phases is required to understand the thermodynamics of the present complicated system.
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CONCLUSIONS
For the first time, we were able to achieve the stereo-controlled growth of a multilayered
supramolecular porous network at a liquid/solid interface. DBA derivatives bearing alkoxy
chains substituted at the 2-position with a hydroxy group were designed to extend the growth
towards the third dimension. Upon forming a self-assembled monolayer, three hydroxy
groups are rotated out-of-plane away from the surface to potentially facilitate hydrogen
bonding interactions with the overlaying layer. Under appropriate concentration and solvent
conditions, double layer formation was confirmed by bias voltage-dependent STM
observations. Both lateral van der Waals interactions and possibly also longitudinal hydrogen
bonds contribute to the formation of multilayers. Based on the experimental evidence, the
formation of homochiral double layers, i.e., bilayer formation, is a stereospecific process, and
the top and bottom layer have the same intrinsic chirality. Surprisingly, the overlaying layer
adopts opposite supramolecular handedness with respect to that of the first layer, highlighting
the complexity of self-assembly pathways and the mechanisms involved in the amplification
of chirality.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge at hppts://pubs.acs.org/doi/…...
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Experimental details, MM Simulations, additional STM images, and synthesis of chiral DBA
derivatives (PDF)
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AUTHOR INFORMATION
Corresponding Author
* steven.defeyter@kuleuven.be
* tobe@chem.es.osaka-u.ac.jp
ORCID IDs
Yoshito Tobe: 0000-0002-1795-5829
Steven De Feyter: 0000-0002-0909-9292
Kazukuni Tahara: 0000-0002-3634-541X
Dmitrii Perepichka: 0000-0003-2233-416X
Rustam Z. Khaliullin: 0000-0002-9073-6753
Zhenzhe Zhang: 0000-0002-9983-7729
Yuan Fang: 0000-0002-4846-1725
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENTS
This study was supported by JSPS KAKENHI (JP15H02164 and JP18H05353 for Y.T. and
JP17K19130 and JP19H04597 for K.T.) and by Center for Emergent Functional Matter
Science, National Chiao Tung University, which are gratefully acknowledged. The authors
also acknowledge financial support from the Fund of Scientific Research Flanders (FWO)
under grant EOS 30489208 and KU Leuven - Internal Funds. The research leading to these
results has also received funding from the European Research Council under the European
Union’s Seventh Frame-work Programme (FP7/2007-2013)/ERC Grant Agreement No.
340324 to S.D.F. The work in Canada was supported by NSERC Discovery Grants (to R.K.
and to D.F.P.).
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TOC:
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