pubs.acs.org/CR
CONTENTS
1. Introduction
2. Basic Concepts Related to Molecular and Supramolecular Chirality
2.1. Conguration and Conformation Chirality
2.2. Induced Chirality
2.3. Helicity or Helical Chirality
3. Characterization of Supramolecular Chirality
3.1. Morphology Observation
3.2. Spectroscopic Methods for Characterization
of Chirality
3.2.1. CD Spectra of Supramolecular Systems
3.2.2. Measurement Aspects
3.2.3. CD Spectra and Interpretation
4. Supramolecular Chirality in Self-Assembled Systems Containing Chiral Molecular Components
4.1. Supramolecular Chirality in Assemblies of
Chiral Components
4.1.1. Amphiphiles
4.1.2. C3-Symmetric Molecules
4.1.3. -Conjugated Molecules
4.1.4. Molecules with Multiple Chiral Centers
4.2. Chirality Transfer in Systems Containing
Chiral and Achiral Molecules
4.2.1. Chirality Transfer through Noncovalent
Bonds
4.2.2. Chirality Transfer from Solvent to Assemblies
4.2.3. Chirality Transfer from Low Molecular
Weight Molecules to Macromolecules
4.3. Dynamic Features and Regulation of Supramolecular Chirality
4.3.1. Solvents
4.3.2. Temperature
4.3.3. Redox Eect Chirality
4.3.4. Photoirradiation
4.3.5. Chemical Additives
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Acknowledgments
References
Review
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1. INTRODUCTION
Chirality is a basic characteristic of living matter and nature.
During the evolution of life on our planet, nature has favored one
kind of chirality, thereby selecting the L-amino acids (with the
exception of glycine) as the main component of proteins and
enzymes and D-sugars as the main components of DNA and
RNA. In addition, chirality is universal and can be observed at
various hierarchical levels from subatomic and molecular to
supramolecular, nanoscopic, macroscopic, and galactic scales.1
Figure 1 illustrates some typical chiral substances and objects at
these various scales.
At a subatomic level, chirality is connected to parity
conservation. Therefore, only left-handed helical neutrinos are
found. At a molecular level, there are a huge number of chiral
molecules in natural system such as amino acids, sugars, and
terpenes, and many synthetic compounds are also chiral.
Furthermore, there are many biological macromolecules or
supramolecular systems with chirality, microorganisms with
helix-shaped viruses, and bacteria such as tobacco mosaic virus
and Helicobacter pylori, respectively, and macroscopic living
systems such as snails. On a larger scale, one nds that many
plants express chiral sense, such as mountain climbing vines. On a
light-year scale, our galaxy system is also chiral.
Among these various levels, chirality at a molecular and
supramolecular level is of vital importance since it is strongly
related to chemistry, physics, biology, materials, and nanoscience, which treat the matter in scales from atomic to molecular
and supramolecular.2 The concept of molecular chirality has long
been recognized and provided guidance in the design of drugs
and functional molecules, while chirality at a supramolecular level
is currently attracting great attention due to rapid developments
in supramolecular chemistry and molecular self-assembly.
Supramolecular chemistry is the chemistry beyond molecules
or the chemistry of entities generated by intermolecular
noncovalent interactions.3,4 Supramolecular chemistry is
strongly related to self-assembly, which has been dened as the
autonomous organization of components into patterns or
structures without human intervention.5 Both molecular selfassembly and supramolecular chemistry are connected by
noncovalent bonds and/or certain nano/microsized architectures. Molecular self-assembly plays an important role in
biological systems, the transfer and storage of genetic
information in nucleic acids, and the folding of proteins into
ecient molecular machines.6 During such biological processes,
supramolecular chirality, which can be simply regarded as
chirality at a supramolecular level, is the result of biological
molecular self-assembly. A typical example is the secondary
structures of proteins, which can exhibit various conformations
such as -helix, -sheet, and random coil structures with dierent
supramolecular chirality. During the molecular self-assembly,
supramolecular chirality is also the result of the special spatial
arrangements of the molecules. Although supramolecular
chirality is strongly related to the chirality of the component
chiral molecules, it is not necessary that all components be chiral.
To this end, achiral molecules can also possibly produce
supramolecular chirality in a self-assembled system. Therefore,
a deeper exploration of chirality at the molecular and
supramolecular level will provide a better understanding of
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Figure 1. Chiral architectures at various scales, from neutrinos to enantiomeric molecules, nanosized biomacromolecules with chiral structures (DNA
and proteins), self-assembled micrometer-sized helical ribbons, microorganisms (helix-shaped bacteria), macroscopic living systems (seashells and
plants), and galaxies. SEM image showing a helix is reprinted with permission from ref 285. Copyright 2014 John Wiley & Sons. The picture of a protein
structure was obtained from Wikipedia (http://upload.wikimedia.org/wikipedia/commons/f/f3/T7RNA_polymerase_at_work.png) and reprinted
under the fair use under Wikipedias license. Pictures are obtained from the following Web sites and apply to fair use: bacteria (http://tech.sina.com.
cn/d/2010-01-29/10113816919.shtml), seashell (http://news.hainan.net/hainan/yaowen/tupian/2014/08/14/2016639.shtml), and ower (http://
www.chla.com.cn/htm/2011/0403/80069.html). The picture of a galaxy is a free stock graphic obtained from http://www.rgbstock.com/bigphoto/
mVErmjU%2FSpiral+Galaxy.
atom
covalent bond
tetrahedron, axis,
plane
point, axis, and
plane
supramolecular chirality
xed chirality,
recognition
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Figure 2. Some typical chiral molecules and their corresponding naming conventions.
Figure 3. (Top) Comparison of various microscopies used to characterize the chiral architectures. (Bottom) (A) AFM images of xerogels self-assembled
from L- and D-HDGA (N,N-hexadecanedioyl-diglutamic acid). Reprinted with permission from ref 27. Copyright 2010 Royal Society of Chemistry. (B)
STM images of the chiral twin chains from PVBA. Reprinted with permission from ref 28. Copyright 2001 The American Physical Society. (C) Mirrorimaged nanorods self-assembled from TPPS and (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane. Reprinted with permission from ref 29. Copyright 2013
Royal Society of Chemistry. (D) TEM image of a chiral twist self-assembled from pyridine-containing L-glutamide. Reprinted with permission from ref
30. Copyright 2011 Royal Society of Chemistry.
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3. CHARACTERIZATION OF SUPRAMOLECULAR
CHIRALITY
An important step in the research of supramolecular chirality is
the characterization of the chirality. Although there are many
ways to characterize the chiral features of a supramolecular
system, two classes of characterization of supramolecular
chirality are usually applied. One is the morphological
observation by various microscopes, with which one can directly
observe the chiral molecules and chiral structures. With the rapid
development of STM, AFM, SEM, and TEM technologies, direct
observation of chiral structures has been made possible, and
these techniques have signicantly assisted in the development of
research on chirality, especially in the self-assembled supramolecular systems. The other class of characterization is
spectroscopy techniques such as circular dichroism (CD),
vibrational CD (VCD), and Raman optical activity (ROA)
spectroscopy. With these techniques, the dynamic features of the
supramolecular chirality can be followed and the self-assembly
process can be unveiled. Although X-ray structural analysis is
useful in determining the absolute conguration of the chiral
molecules, it requires that samples form into crystals. Selfassembly systems are generally not crystallized and thus not
applicable for X-ray crystallography. However, the molecular
conguration and packing information from the X-ray studies
can help in understanding the self-assembly process. Herein, we
do not attempt to explain all of the possible characterization
methods in detail but provide a general introduction as to how
these techniques are applied to the study of supramolecular
chirality.
3.1. Morphology Observation
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4. SUPRAMOLECULAR CHIRALITY IN
SELF-ASSEMBLED SYSTEMS CONTAINING CHIRAL
MOLECULAR COMPONENTS
During the chiral self-assembly, an important issue is how the
supramolecular chirality or the chiral nanostructures are
produced. Propagation of chiral information through specic
interactions and organization in materials or supramolecular
assemblies is generally called chirality transfer. The chirality
transfer from the molecules to the supramolecular system
represents an important origin of supramolecular chirality. This
chirality transfer in self-assemblies containing chiral molecular
components can be divided into two cases: (1) the chiral
information on a chiral center (generally an asymmetric carbon
atom or axial chirality) is imposed to the whole aggregate or
assemblies containing a chromophore, which usually can be
detected by CD spectroscopy, and (2) the chiral sense of one
component is transferred to achiral components to form a
complex system exhibiting supramolecular chirality. The bridges
for this chiral transfer are various noncovalent interactions, such
as hydrogen bonding, electrostatic interactions, metalion
coordination, donoracceptor interactions, hostguest interactions, and van der Waals interactions. In this section, we will
discuss the chirality transfer in systems composed of chiral
molecules and in those containing mixed chiral/achiral
molecules. Chiral systems composed exclusively from achiral
molecules will be the topic of the next section.
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Figure 8. AFM images of hydrogels of (A) 15c, (B) 18, and (C) 19.
Reprinted with permission from refs 72, 74, and 75. Copyright 2005 and
2013 Royal Society of Chemistry and Copyright 2013 John Wiley &
Sons.
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show strong CD signals in their absorption regions via selfassembly, which means the chirality can be transferred from the
periphery to the core and the whole assembly. A helical tube
fabricated from a dendritic glutamide lipid87 (21) exhibited a wall
with a thickness of 4 nm, which corresponds to a bilayer thickness
(Figure 11). While many other compounds generally form
multiwalled nanotubes, these dendron molecules appeared to
form a double-walled nanotube, because of the multiple H bonds
between the dendron heads that stabilize the bilayer structures.
More interestingly, the nanotube structure is very stable in a wide
pH range.
4.1.2. C3-Symmetric Molecules. Among the many supramolecular building motifs, C3-symmetric molecules have gained
special interest in forming organized nanoassemblies either
chirally or nonchirally.88,89 C3-symmetric building blocks, usually
consisting of a central aromatic or cyclohexane ring functionalized at the 1, 3, and 5 positions, have been frequently exploited.
In the design of the C3-symmetric molecules, other functional
groups can be attached via amide or urea bonds with tricarboxylic
acids or triamines. If chiral elements are introduced into these
molecules, chiral supramolecular assemblies can be easily
obtained. The C3-symmetric molecules often adopt a propellerlike conformation, because of the steric hindrance surrounding
the central aromatic core and the wedged substituent group
which causes rigidity through intramolecular interactions
(mainly hydrogen bonding). During stacking, the chiral elements
play an important role in determining the chiral sense of the
assemblies. The benzene-1,3,5-tricarboxamide (BTA) motif
comprising either three N-centered or three CO-centered
amides attached to a benzene core (Figure 12) has been widely
employed in the assembly of chiral supermolecules. The three
amide bonds in these molecules form H bonds, which contribute
to the one-dimensional growth of the monomers into a
columnar-type supramolecular polymer. The chiral information
at the substituents of the molecule can be transferred to the
central aromatic rings and induce preferential formation of a
single helicity in their supramolecular architectures. During this
process, chirality transfer is largely dependent on the size of the
C3 core and the connection between the wedged substituents
and the core.
Figure 10. Structures of the isomeric peptide amphiphiles, and a schematic illustration of the nanostructures formed. Reprinted with permission from ref
80. Copyright 2014 American Chemical Society.
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Figure 11. Structure of dendron amphiphiles (left) and height AFM images of hydrogels of 21 (right): (A) pH 3, (B) pH 7, (C) pH 10, (D) pH 11. (E)
AFM image analysis of the helical pitch. (F) TEM image of a hydrogel obtained at pH 7. AFM and TEM images reprinted with permission from ref 87.
Copyright 2011 John Wiley & Sons.
Meijer et al. presented pioneering work on the chiral selfassembly of BTA molecules.9093 The self-assembly of the parent
compound, CO-centered BTA equipped with chiral aliphatic
side chains, has been found to self-assemble into helical, onedimensional aggregates by means of strong, 3-fold H bonding,
which was conrmed by a strong Cotton eect centered around
220 nm. Later, several groups extended these studies by
synthesizing BTA derivatives with increased surfaces.
Examples include bipyridine,94,95 tetrathiafulvalene (TTF),96
NDI,97and porphyrins98,99 substituted with chiral side chains,
which were connected to the BTA core. Due to the large
conjugated surface, intermolecular self-assembly in solution takes
place via strong interactions and solvophobic eects.100
The self-assembly of N-BTAs shows self-assembly behavior
that is similar to that of their CO-centered counterparts, but
the amplication of chirality is less pronounced as the result of
the relatively weaker aggregation. A theoretical simulation reveals
that there is a higher energy penalty for rotation around the Ph
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Figure 13. Structures of CO-centered BTAs having intramolecular hydrogen bonds with increased surface.
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for 40. While the number of amide bonds was the same in both
systems, the strength of the hydrogen bonding varied. Combined
with the weaker stacking interactions in the C2-symmetric
discotics relative to the C3-symmetric discotics, the chirality
transfer may have occurred in a dierent manner.
The chirality of the chiral center can further be transferred to
determine the supramolecular chirality of the nanostructures.
For example, enantiomeric C3 compounds containing functional tetrathiafulvalene units (compound 31) selfassembled into helical aggregates showing a preferential helicity
twist over several length scales (Figure 17).96 The formation of
primary helices as twisted stacks was investigated by CD
measurements and further conrmed by the theoretical
calculations. molecular mechanics (MM) and molecular
dynamics (MD) simulations were used to evaluate the relative
stability of the P and M conformations of the stacks, and the
results indicated that the (S)-31 enantiomer provided the M
helix, which showed greater stability (2 kcal mol1) per molecule
than the P helix, which was in agreement with the optical activity
observed in the CD spectra. However, it was a surprise to obtain
mesoscopic-size chiral bers of this compound in higher
concentrations, which exhibited inverted helicity, i.e., P helices
for the S enantiomer and M helices for the R one. Although the
inversion of helicity between the primary twisted stack in
solution and the secondary helical aggregates for the solid bers,
which can be seen as superhelices from hierarchical assembly,
seems to be incomprehensible, it is a common phenomenon that
has been reported in many supramolecular systems. A more
detailed and exhaustive study needs to be conducted to explore
the link between molecular chirality, supramolecular chirality,
and the higher order of chiral expression or chiral nanostructures.
C3-symmetric benzene- or cyclohexane-centered chiral molecules often self-assemble into nanotube structures by column
stacking of the assembly unit. When chiral units are introduced,
the self-assembly process and formation of the nanotubes seems
to be easier. For example, a C3-symmetric L-glutamic acid ethyl
Figure 15. (A) Structures of C3-symmetric BTAs (35) and triangleshaped OPETAs (36). (B) CD spectra of compound 36b (2.5 106 M
in MCH) at room temperature and 90 C. Insets depict the cooling
curves of compound 36b from 363 to 288 K at intervals of 0.5 K min1.
Reprinted with permission from ref 102. Copyright 2013 John Wiley &
Sons.
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chiral feature of the building unit itself, the substituent group, the
nature of the -conjugated backbone, solvent properties,
temperature, and even the stimuli factors such as light, heat,
sonication, magnetic elds, etc., can have a signicant inuence
on the chiral assemblies. Herein we demonstrate the typical chiral
assembly features for important -conjugated molecules such as
polycyclic aromatic hydrocarbons, thiophene and its derivatives,
oligo(p-phenylenevinylene) (OPV) and its derivatives, and
perylene bisimide (PBI) and its related compounds. Since the
self-assembly of a -conjugated molecule in a gel has been
reviewed,111,112 herein we focus on those materials with
supramolecular chirality.
4.1.3.1. Pyrene (a Polycyclic Aromatic Hydrocarbon). The
pyrene moiety is well known for its ability to form excimers at
specied concentrations in solution. In addition, the strong
stacking of the chromophore makes it easy to perform selfassembly, during which supramolecular chirality can also be
observed in the CD spectra if the chiral unit is introduced in the
vicinity of the chromophore. For example, compounds 42 and 43
contain a pyrene moiety covalently connected to the chiral unit
through the urethane moiety, forming organogels in isooctane
and n-dodecane, respectively. Although the solution of the
compounds did not show a CD signal, they exhibited CD signals
at gel states in the region of pyrene chromophores, indicating
that the chirality was transferred from the asymmetric carbon
atom to the whole assembly. A temperature-dependent CD
spectrum indicated that as the gel was progressively heated, the
CD signal decreased and completely disappeared as the gel
melted (Figure 18b), suggesting that chiral supramolecular
assembly was responsible for the CD signal.113
Two pyrene-conjugated glutamide derivatives were designed
to investigate the eect of the link spacer on the chirality transfer.
The pyrene moiety was linked to amphiphilic L-glutamide
directly (4a) or with three methylene spacers (4b). In both
Figure 18. (a) CD spectra of isooctane gels of 42R (solid line) and 43R
(dotted line) at 293 K (1 mm path length). (b) Variable-temperature
CD spectra on an isooctane gel of 43R (31 mM). Reprinted with
permission from ref 113. Copyright 2010 American Chemical Society.
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electronic and photonic devices through the formation of selfassembled structures. There are many reports on the emergence
of supramolecular chirality based on PBIs as building units.115,116
For example, the aggregates of dipeptides and perylene
bisimide conjugates (glycine-tyrosine, GY, or glycine-aspartic
acid, GD) have been reported to show dierent chiral selfassembly depending on the nature of the peptide used. There is a
competition between H bonding among the peptides and the
aromatic stacking of PBI. Most interestingly, the peptide
sequence has a profound eect on the chirality transfer. In an
aqueous buer, PBI-[GY]2 formed chiral nanobers. In the
corresponding CD spectra of PBI-[GY]2 aggregates, a negative
Cotton eect at 447 nm and two positive Cotton eects were
observed at approximately 515 and 552 nm, indicating that the
chiral sense of the peptide was transferred to the PBI moiety. By
contrast, the PBI-[GD]2, which formed spherical aggregates
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Figure 23. (A) Structures of 47 and 48. (B) CD spectra of S-48 in aqueous solution at various concentrations. (C) Temperature-dependent CD spectra
of S-48 (0.01 wt %) in aqueous solution. (D) Schematic representation of reversible switching of the tubules between expanded and contracted states
with chirality inversion. Reprinted with permission from ref 122. Copyright 2012 American Association for the Advancement of Science.
Figure 24. Structures of 4952, and schematic illustration of the aggregation pathways. At low concentrations, low temperatures, and short times, the
helical organization of 50 is dominated by the atropisomerism of the central biphenyl unit and metastable P-type helices are formed. 51 and 52, and also
50 at higher concentrations, higher temperatures, and longer times, self-assemble into supramolecular structures of the opposite helicity (M-type).
Reprinted with permission from ref 123. Copyright 2013 John Wiley & Sons.
phenyl ring in the core.123 The OPPS with more than two phenyl
rings in the core self-assembled into left-handed helices, but
when it contained a biphenyl core the resulting molecule showed
exchangeable helicity depending on the reaction time, temperature, and concentration, exhibiting a competitive modulation of
supramolecular helicity controlled by a kinetic versus thermodynamic process. At low temperature, low concentration, and short
assembling times, compound 50 formed right-handed metastable
supramolecular helices under kinetic control. In this case, the
supramolecular chirality was determined by the axial chirality of
the biphenyl core. On the contrary, at higher temperature, higher
concentration, and longer reaction times, the external S
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room temperature, 53 was molecularly dissolved in chloroformand. It had a sharp Soret band at max = 422 nm but lacked a CD
signal. In MCH, porphyrin 53 exhibited a large blue shift to a
broadened band at max = 390 nm, which is a typical band
observed for cofacially arranged porphyrins or H aggregates.125
The CD measurements revealed an intense bisignate Cotton
eect with a crossover at 390 nm, indicating a helical
arrangement of the chromophores in the aggregate. The
porphyrin assemblies were disrupted by heating, accompanied
by a disappearance of the CD response. Upon cooling at a
concentration of 5.0 105 M, the CD eect reappeared at 69 C
(Figure 25).
A unique property of porphyrin compounds is their axial
coordination ability. Changes of the axial ligand will cause the
supramolecular chirality of the system to be regulated. For
example, the addition of the axial ligand pyridine to aggregates of
53 was found to alter the supramolecular chirality of the system.
Without pyridine, the porphyrin Soret band appears at 390 nm.
When 40 equiv of pyridine was added, a new red-shifted and split
band at 418 and 427 nm appeared. The exciton splitting energy
of 500 cm1 is indicative of a dimeric porphyrin pyridine
adduct.126 With the dissociation of porphyrin aggregates, the CD
spectrum in the exciton split band region became weak.
Ultimately, at a pyridine molar excess of 80 000, this split Soret
band gradually converted into a single, narrow, CD-silent band at
430 nm. This band was identical in shape and position to a
monomeric porphyrin pyridine adduct,127 which suggested that
at this rather high pyridine concentration, the porphyrin
aggregates have dissociated.
Another feature of the porphryin derivatives is their
modication in the central core by metal ions. A porphyrinato
zinc complex covalently linked with a peptide was designed and
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Figure 26. (Left) Structures of Oxa-OPV, Oxa-6D, Oxa-7O, and Oxa11D. (Right) CD spectra of Oxa-6D, Oxa-7O, Oxa-11D, and Oxa-6D
mono. A representative absorption spectrum for Oxa-11D is also shown.
Reprinted with permission from ref 131. Copyright 2008 American
Chemical Society.
mono (equipped with a single Oxa-OPV) showed no excitoncoupled CD signal. Oxa-6D and Oxa-7O, both of which have two
Oxa-OPVs with dierent orientations, generated very similar
negligible positive split Cotton eects. The weak Cotton eect
might be due to the high degree of overlap of the side
chromophores for Oxa-6D and the isolated Oxa-OPVs for Oxa7O. Oxa-11D equipped with two chromophores on the same side
with a lager spacing than Oxa-6D showed negative Cotton eects
with the greatest intensity among the three molecules. This
strong CD intensity suggested that the side chains of Oxa-11D
were in sucient proximity to one another for exciton coupling.
Chiral assemblies obtained from OPV polymers have also been
investigated.132 It was found that the chiral polymers (Rac and R)
with both high and low molecular weight could form helical
Figure 27. Structures of chiral oligothiophenes, and (a) CD spectra of T5S, T6S, and T7S in butanol (2.6 105 M) at 283 K. (b) CD spectra for all
chiral T6 derivatives (8 105 M) at 283 K. Reprinted with permission from ref 134. Copyright 2006 American Chemical Society.
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Figure 28. Inuence of the addition of methanol to a chloroform solution of the block copolymers 5457. (AD) CD spectra of compounds 5457 in
mixtures of methanol and chloroform. Reprinted with permission from ref 138. Copyright 2010 American Chemical Society.
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Figure 32. Molecular structure of pyridine-end OPV 62, AFM topographic images showing (i) M helix for 62 + L-TA, (ii) P helix for 62 + D-TA, and (iii)
a mixture of M and P helices for 62 + M-TA. Reprinted with permission from ref 147. Copyright 2012 Royal Society of Chemistry.
Figure 33. Structures of tetracarboxymetallophthalocyanine 63 and chiral amines. Reprinted with permission from ref 149. Copyright 2011 John Wiley
& Sons.
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control over a large length scale from molecules to nanostructures could have implications in the design of asymmetric
nanocatalysts.
4.2.1.3. MetalLigand Coordination. The interactions
between metals and ligands are at the heart of a wide variety of
chemical, physical, and biological phenomena. Metalligand
interactions allow the design of materials with controlled
topology and with specic physical properties such as redox,
magnetic, or photochemical properties. Combined with a chiral
sense, metal-based materials can be designed that have unique
properties including chiroptical properties (circular dichroism
Figure 35. Structures of OPVs 65, thymidine, and thymine. Reprinted with permission from refs 151 and152. Copyright 2011 and 2013 American
Chemical Society. Reprinted with permission from ref 153. Copyright 2014 Royal Society of Chemistry.
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Figure 36. Poly(p-phenylene) derivative (PPP) 66 and binaphthyl derivatives (BNPs) with (R)- and (S)-congurations. A plausible model of the
electrostatic and interactions between two 66 repeating units and one (R)-BNP molecule. (a) UVvis absorption, CD, and gabs spectra, and (b) PL,
CPL, and glum spectra of PPP, BNP, and a mixture (PPPBNP) (1.0:2.0 mol/mol) in methanolwater (50:50 v/v). Reprinted with permission from ref
155. Copyright 2012 John Wiley & Sons.
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Figure 37. (Top) Structures of TPPS (67) and chiral amines. (Bottom)
(A and B) Typical SEM images of the 67 (TPPS) nanostructures
assembled with the assistance of R-DAC (A) and S-DAC (B). (C) UV
vis (bottom) and CD (top) spectra of the dispersion of TPPS obtained
in the presence of R-DAC (black) and S-DAC (red). (DG) Typical
TEM and HRTEM images of the TPPS nanostructures assembled with
the assistance of R-DAC (D and E) and S-DAC (F and G). (Inset in
panels E and G) FFT of the corresponding HRTEM image. TPPS/DAC
ratio is 1/4. At the bottom is a schematic illustration of the formation of
mirror-imaged 67 nanorods with the assistance of DAC molecules.
Reprinted with permission from ref 29. Copyright 2013 Royal Society of
Chemistry.
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Figure 40. Structure of oligothiophene derivative 69; CD spectra of the gel phase of 69 (straight line), 69(R,R)-diammonium (dashed line; triangle),
and 69(S,S)-diammonium (dotted line; circle). (a) ICD spectra of the 1:1 mixture. (b) CD titration study at 370 nm. Reprinted with permission from
ref 162. Copyright 2012 John Wiley & Sons.
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Figure 41. Structures of (A) dopant Schi base compound 70 and (B)
2L and 2D. (C) Schematic illustration of their coassembly. (a) A Schi
base based on a dynamic covalent bond. (b) In the coassembly of 70 and
2, 70 can be inserted into the alkyl chains of 2 molecules. On the basis of
hydrophobic interactions, a supramolecular assembly with twist
structure can be formed, and the supramolecular chirality can be
transferred from 2 to the Schi base moiety. The supramolecular
chirality showed on and o states through the alternate treatment of
acid and base. Reprinted with permission from ref 163. Copyright 2013
Royal Society of Chemistry.
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Figure 42. Schematic illustration of chiral induction by helical neighbors. Reprinted with permission from ref 164. Copyright 2011 Royal Society of
Chemistry.
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Figure 43. Molecular structure of PBI derivative 73. AFM images of a lm spin coated (2000 rpm) from a solution of PBI 1 in (S)-limonene (c = 1 104
M) onto HOPG. (a and b) Height images. (c) Phase image. Scale bars in a and c correspond to 450 nm; the z scale in a and b is 9 nm. The statistical graph
of M and P helices is derived from image a. (ab and cd) Cross-section analyses of the bers. Reprinted with permission from ref 169. Copyright 2013
John Wiley & Sons.
Figure 44. Schematic illustration of the preferential chiral solvation in OPVUT self-assembled stacks. Reprinted with permission from ref 144.
Copyright 2011 Royal Society of Chemistry.
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Figure 45. Schematic illustration of unpolarized-light-driven chiroptical switching in CHCl3/(1R or 1S)/IPA (0.3/1.5/1.2, v/v/v). In 74-trans, chiral
aggregation manifested as a bright yellow and turbid solution, while nonaggregated 74-cis formed a yellow transparent solution. Reprinted with
permission from ref 172. Copyright 2011 American Chemical Society.
Figure 46. Schematic illustration of helical polymers obtained from achiral polymers induced by achiral guests and structures of poly(phenylacetylene)s,
poly(thiophene)s, and poly(phosphazene)s. Reprinted with permission from ref 174. Copyright 2009 American Chemical Society.
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Figure 52. Photoisomerization of the azobenzene-linked phenyleneethynylene derivatives 82 and 83. A mixture of E,E, E,Z, and Z,Z isomers is possible.
SEM images of (S)-83 (a) before and (b) after photoisomerization; AFM images for (S)-83 (c) before and (d) after photoisomerization. Reprinted with
permission from ref 203. Copyright 2012 John Wiley & Sons.
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Figure 53. (A) Schematic illustration of the self-assembly of 84. (B) Photoinduced (a and b) UVvis and (c and d) CD spectral change of 84 (c = 3.0
104 M) in MCH at 20 C. (a and c) Changes upon irradiation of a trans-rich solution with 365 nm UV light. (b and d) Changes upon irradiation of the
cis-rich solution with 470 nm visible light. (e) Plots of the fraction of cis-azobenzene moieties (red marks, left axis), and maximum values (blue marks,
right axis) versus irradiation time of UV (left side) and visible (right side) light. Aggregation states are shown with graduated background colors
representing monomeric (water blue) and aggregated (orange) states. Reprinted with permission from ref 204. Copyright 2012 American Chemical
Society.
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Figure 54. (A) Molecular structure of pillar[5]arene, competitive guests (G1 and G2), and a competitive host ([24,8]). (B) Representations of (a) the
planar chiral inversions triggered by achiral guest G1 and (b) alternating addition of achiral guest G2 and host [24,8]. Reprinted with permission from ref
209. Copyright 2013 John Wiley & Sons.
G2 and pillar[5]arenes than those between G1 and pillar[5]arenes. More interestingly, G2 could be removed from the cavity
of pillar[5]arenes with the assistance of the crown ether
[24]crown-8 ([24,8]), resulting in CD intensities that nearly
recovered to their initial state. This result displayed the host
guest complexation as a valid driving force for the chiral
inversion, and this guest-triggered chiral inversion system will be
useful for chiral switching or sensing systems.
Naphthalene diimide amphiphiles functionalized with the
dipicolylethylenediamineZn motif were synthesized in order to
promote a guest-induced self-assembly and chiral induction
through specic binding interactions.210 Titration of NDPA
amphiphiles with increasing molar ratios of ADP resulted in the
gradual evolution of strong Cotton eects, indicating that ADP
binding induced a preferred helical handedness to the resulting
assemblies of achiral NDIs. The binding of ATP induced
opposite handedness to NDI assemblies, as evident from the
positive bisignated CD signal, with positive and negative maxima
at 390 and 359 nm, respectively. The mirror-image Cotton
eects of NDPA-Bola assemblies obtained with ADP and ATP
indicated the induction of chirality with opposite handedness.
Interestingly, addition of 0.5 equiv of ATP to NDPA-Amph/
ADP assemblies resulted in positive bisignated CD signals which
exactly match with those of NDPA-Amph/ATP stacks alone.
This clearly suggested the competitive replacement of ADP by
ATP from the assemblies as expected and an instantaneous
reversal of its helical handedness. The authors also revealed a
dynamic helix reversal procedure through an intrastack
mechanism.
4.3.6. Sonication. Ultrasound is often used as a source of
energy to cleave and homogenize H-bonding, stacking, and
hydrophobic interactions of molecular building blocks and to
reshape the packing mode and the morphology.211216
The self-assembly of bichromophoric perylene bisimide into
chiral nanostructures, and the supramolecular helicity of the
nanostructures could be controlled by varying the method of
Figure 55. (a) CD spectra and (b) schematic of the dynamic helical
reversal of NDPA-Amph/ADP assemblies upon competitive guest
binding experiments with ATP (c = 7 105 M, 70% aq HEPES buer in
THF). Reprinted with permission from ref 210. Copyright 2012 Royal
Society of Chemistry.
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Figure 57. AFM images of prion brils grown in pH 2.0 (a) and 3.9 (b).
Reprinted with permission from ref 220. Copyright 2014 American
Chemical Society.
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Figure 59. (a) Hydrophobic disc-shaped compounds with bipyridine units (32ac). (b) Amplication of chirality observed upon mixing solutions of
32a and 32b in hexane results in a nonlinear relationship between the CD eect and the amount of chiral 32a added to achiral 32b. (c) Net helicity as a
function of enantiomeric excess measured by CD spectroscopy of mixtures of 32a and 32c in n-octane. The line indicates the theoretical result that gives
the closest agreement with the experiment. Reprinted with permission from ref 96. Copyright 2011 American Chemical Society.
Figure 60. Coronene bisimide molecules 85 and 86 and coassembly of 85 and 86 and resultant chiral amplication. All experiments were done in MCH
(c = 2.5 105 M). (a) CD spectra of the coassembly at dierent percentages of 85 in a 1 cm cuvette at 20 C. The arrow indicates the spectral change
with an increase in the percentage of the sergeant. (b) Anisotropy value or g value monitored at = 320 nm as a function of the percentage of 85. The
dashed line that connects the fraction of 85 indicates the linear variation of the g value in the absence of any chiral amplication. Reprinted with
permission from ref 223. Copyright 2013 John Wiley & Sons.
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Figure 61. CD spectra of mixtures of (R)-89:88 (A), (R)-90:88 (B), and (R)-91:88 (C). Net helicity versus fraction of sergeant for mixtures of (R)89:88, (R)-90:88, and (R)-91:88 (D). Reprinted with permission from ref 224. Copyright 2010 American Chemical Society.
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Figure 62. (A) Molecular structures of the porphyrin trimers 9396. (B) Schematic representation of the self-assembly of porphyrin trimers in helical
columnar stacks. Reprinted with permission from ref 99. Copyright 2012 Royal Society of Chemistry.
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Figure 63. (a) Chemical structures of 97 and CA. (b) Proposed structure of 3:1 hydrogen-bonded complex 97SCA. (c) Schematic illustration of helical
columns. Reprinted with permission from ref 228. Copyright 2011 John Wiley & Sons.
The phenomenon of chirality memory describes a supramolecular system in which chirality is rst induced and then
maintained after the chiral source is erased or replaced by an
achiral component. Thus, these complexes have a memory for
the chirality of the species that induced the systems asymmetry
after the removal of these inductor molecules.
Generally, chiral memory is dicult to induce in noncovalent
supramolecular assemblies, partly because additives often
interfere with the noncovalent interactions that hold the
assembly together. However, in recent decades, more eorts to
explore supramolecular chirality memory systems have proven to
be successful through the eorts to design the chiral and achiral
units and control the dynamics. In order to realize the chiral
memory, there are several important elements. First, the induced
chiral nanostructure should be generally stable. Thus, even when
you remove the chiral species, the chirality is maintained. Second,
a small amount of the chiral substance should be able to induce
chirality in the system. A successful chiral memory system may
contain (1) noncovalently induced helical polymers, (2) strong
aggregates from achiral building blocks such as J or H aggregates,
or (3) chiral cages from coordination compounds.
4.5.1. Helicity Memory in Noncovalently-Induced
Helical Polymers. Helicity memory in the noncovalently
induced helical polymers has been thoroughly investigated by
Yashima and co-workers.174 On the basis of a chiral memory
system of noncovalent helicity induction in optically active
polymers, Yashima et al. developed an excellent macromolecular
memory system of a helical polyacetylene in the solid state.231
They synthesized a polyacetylene derivative, 101, and induced its
preferred-handed helicity in the presence of (S)-phenylethanol in
n-hexane through weak hydrogen-bonding interactions. 101 was
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Figure 65. (A) G values centered at 309 and 255 nm as a function of the
ee value of nonequimolar mixtures of 100L and 100D. The G value of
the racemate was set to zero. (B) SEM images of the nanostructures
formed from mixtures of 100L and 100D with various ee values.
Reprinted with permission from ref 230. Copyright 2013 John Wiley &
Sons.
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Figure 67. Assumed mechanism of helix stabilization of methynylpyridine host oligomer 102 by coordination of copper and
phen inside the helix. Reprinted with permission from ref 232.
Copyright 2012 Royal Society of Chemistry.
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Figure 70. Schematic illustration of a series of experiments for investigating the dynamic nature of nanotubularly assembled HBCPy. Reprinted with
permission from ref 246. Copyright 2013 American Chemical Society.
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Figure 73. (A) Structure of the dimeric building block of BPCA-C7PmOH 105. (B) Chiral propellers from the self-assembly of this achiral
molecule 105 (BPCA-Cn-PmOH). Reprinted with permission from ref
257. Copyright 2006 John Wiley & Sons.
Figure 75. (A) Structure and phase sequence upon cooling of the four
B4 phase-forming compounds studied. (B) Mechanism and TEM
images of hierarchical self-assembly of the nanolament (NF) phase
starting with bent-core mesogenic molecules. Reprinted with permission
from ref 259. Copyright 2009 The American Association for the
Advancement of Science.
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Figure 77. (A) Molecular structure and phase sequence of PnOPIMB (112) (n = 7, 8, 9 and 12) during cooling at 1 C min1. (B) TEM image and
models showing the double-twist structure. Reprinted with permission from ref 262. Copyright 2014 Nature Publishing Group.
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Figure 79. Schematic illustration showing the controlled synthesis of various porphyrin nanostructures with varied supramolecular chirality by means of
an SAS, where an oil/aqueous medium was employed. CD spectra of ZnTPyP (114) nanorods fabricated in sample B that was aged for 3 days. Black and
red curves are the results detected from the samples prepared in dierent batches. Reprinted with permission from ref 270. Copyright 2010 American
Chemical Society.
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ments show that only the slow aggregation process can lead to
supramolecular chiral assembly (Figure 83).
For symmetry breaking upon the self-assembly of achiral
building blocks, a recently published THF/water system is worth
mentioning. Since THF and water are not completely miscible, a
liquid/liquid interface is present in THF/water mixtures with
volume ratios of 1/1. When a THF solution of achiral carboxyl
azobenzene derivatives (Figure 84A) was added dropwise to an
aqueous solution of melamine, supramolecular chiral assemblies
can be obtained at the THF/water interface along with the
permeation and volatilization of THF (Figure 84C).274 For the
formation of coassemblies, hydrogen bonding between carboxyl
azobenzene derivatives and melamine plays a very important
role. TEM and AFM measurements show that these assemblies
are long and helical bers with intrinsic conformational chirality
(Figure 84B). Furthermore, the morphology and chirality of the
supramolecular assemblies are photoresponsive, which is
induced by the photoisomerization of the azobenzene
components within the self-assembled nanostructures.
For supramolecular chirality from an assembly of achiral
molecules in solution, it seems that -conjugated molecules are
always necessary. Within these self-assemblies, the aromatic rings
tend to overlap through stacking. Thus, the displacement of
aromatic rings within the molecular packing shows a slight angle
between neighboring rings, which will produce a chiral bias. If
this bias is repeated by forming a helix in a certain direction,
supramolecular chirality would emerge and be amplied.
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Figure 82. (A) Molecular structure of achiral bolaamphiphilic azobenzene 117 and its packing mode within the self-assembly. (B) (a) TEM and (b)
SEM observation of the self-assembled coiled and tubular nanostructures of 117 from water at pH 2.77. (c) TEM image of the twisted ribbon. (d) HRTEM image of the nanotube. (C) CD spectra of the self-assembled suspension 117 at pH 2.77 (solid line) and 117 itself (dashed line). Reprinted with
permission from ref 199. Copyright 2012 The Royal Society of Chemistry.
Figure 83. (A) Molecular structure of TPPS (67). (B) Schematic illustration showing kinetic control of the supramolecular chirality of the assembly of
acidied TPPS with J aggregation. Reprinted with permission from ref 273. Copyright 2014 American Chemical Society.
Figure 84. (A) Chemical structures of carboxyl azobenzene derivatives and melamine, and the schematic representation of their complex. (B) (a, b)
TEM and (c and d) AFM observation of the self-assembled helixes and supercoils with labeled handedness. (C) CD measurements of the assemblies.
Reprinted with permission from ref 274. Copyright 2014 The Royal Society of Chemistry.
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Figure 86. Formation of optically active supramolecular gels with chiral nanostructures and optical activity by the hierarchical self-assembly of achiral
119. Reprinted with permission from ref 284. Copyright 2014 John Wiley & Sons.
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Figure 87. (A) Chemical structures of NpImC17 (120), and the model for the formation of the chiral NpImC17Ag(I) coordination assemblies. (B)
Circular dichroism (CD) (A) and UV (B) spectra of a 10-layer NpImC17 LB lm transferred from the pure water surface (a) and a 20-layer Ag(I)
NpImC17 LB lm (b). Reprinted with permission from ref 39. Copyright 2003 American Chemical Society.
Figure 88. (A) Structure of achiral amphiphilic barbituric acid 121. (B) AFM images of one-layer LB lms deposited at various surface pressures at 20 C
(a) and (b) 7, (c) 20, and (d) 30 mN/m after the inection point. Reprinted with permission from ref 285. Copyright 2004 American Chemical Society.
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Figure 90. (A) Structure of 4-octyl-4-(5-carboxypentamethyleneoxy)azobenzene (trans-C8AzoC5, 124). (B) Formation of optically active
and inactive supramolecular assemblies from trans-C8AzoC5 (top, 124)
and cis-C8AzoC5 (bottom), respectively. Reprinted with permission
from ref 288. Copyright 2006 American Chemical Society.
Figure 91. (A) CD spectra of 20-layer LS lms of (a) ODA, (b) CTAB,
and (c) DOAB with TPPS transferred at 30 mN/m. (B) Schematic
illustration of TPPS/amphiphile coassemblies and the J aggregation of
TPPS. Reprinted with permission from ref 289. Copyright 2003
American Chemical Society.
Figure 93. (A) Structure of amphiphilic diacetylene derivative (tricosa10,12-diynoic acid, TDA, 125). (B) UVvis and CD spectra of LB lms
deposited from in situ photopolymerized PDA lms (a) from pure water
and (b) from Cu(NO3)2. (C) TEM images of PDA lms in situ
polymerized on pure water. Reprinted with permission from ref 292.
Copyright 2002 The Royal Society of Chemistry.
Figure 92. Protonation of achiral water-insoluble free-base porphyrins can lead to optically active supramolecular assemblies at the air/water interface.
Reprinted with permission from ref 290. Copyright 2007 John Wiley & Sons.
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Figure 95. (A) Molecular structures of dierent porphyrin derivatives. (B) Possible stacking of the porphyrin TPPA3 (133) and TPPA0 (129) assembly
on the air/water interface. Reprinted with permission from ref 296. Copyright 2008 The Royal Society of Chemistry.
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Figure 98. (A) Structure of 5-phenyl-10,15,20-tris(4-sulfophenyl)porphyrin (135). (B) AFM images of assemblies of 135 showing the onset of folding
in stagnant and stirred solutions. Reprinted with permission from ref 299. Copyright 2006 John Wiley & Sons.
Figure 99. (A) J aggregation of achiral dendritic zinc porphyrin (136) and macroscopic chirality from spinning. (B) Mechanism for the formation of
chiral assemblies. Reprinted with permission from ref 248. Copyright 2004 John Wiley & Sons.
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Figure 106. (ad) Self-assembly leading to the formation of a twodimensional emulsion featuring chirally resolved domains. transAzobenzene surfactant molecules (b, 141), resulting from the
spontaneous isomerization of the cis isomer (a), self-assemble at the
air/water interface into segregated chirally resolved circular domains
surrounded by the cis-rich matrix (d); (e) molecular structures of achiral
trans-azobenzene surfactant 141 and its chiral analogues 142 and 143.
(f) Coupling between the chiral modier and the vortical ow.
Reprinted with permission from ref 306. Copyright 2012 Nature
Publishing Group.
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Figure 109. (A) Structure of discotic hydrogen-bonding complex of diacetylene (DA) units. (B) Asymmetric polymerization of the corresponding
complex by using linearly polarized light irradiation and a magnetic eld. Reprinted with permission from ref 310. Copyright 2014 The Royal Society of
Chemistry. Reprinted with permission from ref 311. Copyright 2014 Nature Publishing Group.
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Figure 112. Chiral self-sorting during supramolecular helical organization of hat-shaped molecules. Reprinted with permission from ref 319. Copyright
2014 American Chemical Society.
The gelation properties, supramolecular chirality, and nanostructures of the racemic hydrogels can be regulated by changing
molar ratios of dierent molecular building blocks (Figure
115).323
In addition to forming supramolecular gels, the mixing of
enantiomers has also been used to tune the properties of dierent
supramolecular assemblies. Oda et al. studied the twists and
nanotubes formed from the coassembly of nonchiral dicationic n2-n Gemini amphiphiles with chiral tartrate anions. They found
that the morphologies of the assemblies, such as the twist pitch of
the ribbons, can be continuously modulated by varying the
enantiomeric excess of tartrate anions. For instance, adding 10
mol % of the opposite enantiomer of tartrate anions led to a 15%
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Figure 117. (A) Correlative plot of the vibration bands of NH, amide
I, and amide II and the d spacing of the nanostructures in the mixed gels
against the enantiomeric excess value (ED/L). (B) Proposed mechanism
for the formation of various nanostructures upon mixing enantiomeric Lor D-glutamic-acid-based lipids. Reprinted with permission from ref 53.
Copyright 2010 John Wiley & Sons.
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Figure 118. (A) Molecular structure of the enantiomeric alanine derivatives AlaC17 (100). (B) Schematic illustration of the molecular packing for a
single enantiomer and the racemate. The backgrounds are the SEM images of the transparent hexane gel formed by L-AlaC17 and the twisted ribbons
formed by the racemic mixture. (C) Intensity of the CD signals (centered at 309 nm) of the racemate upon addition of 2 mol % of various amino acid
derivatives. LBG is a glutamic acid derivative with two long alkyl chains. Reprinted with permission from ref 230. Copyright 2013 John Wiley & Sons.
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Figure 124. (A) Molecular structures of the HQLG ligand molecule (10) and its metal complexes. (B) Chiral recognition brought about by the
metallogels. Reprinted with permission from ref 55. Copyright 2013 American Chemical Society.
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Suzuki et al. synthesized secondary terephthalamide derivatives containing four aryl blades (153a-H), which can be used as
the host molecule for chiral sensing. The conformation of this
host can be changed from a nonpropeller anti form to a propellershaped syn form with the formation of a complex with some
chiral molecules, such as p-xylylenediammonium derivatives.
Moreover, depending on the chirality of the guest enantiomers
coassembled with secondary terephthalamide derivatives, the
complex can be biased to prefer a particular handedness, with the
enhancement of CD signal. This secondary terephthalamide
derivative can be used as chiral sensor for the discrimination of
the very important neurotransmitter, ()-phenylephrine (Figure
128).369
Some biomacromolecules can also be used for chiral
recognition and sensing systems. As one of the most important
biomacromolecules, DNA contains chiral information from the
molecular to supramolecular level. Moreover, the stability of
DNA can be a huge advantage for building dierent devices for
chiral sensing.
Qu et al. constructed electrochemical DNA sensors for the
chiral sensing. In this system, DNA molecules modied with thiol
groups were covalently bonded to a gold electrode. When small
chiral molecules interacted with DNA, changes in the electrochemical characteristics of the gold electrode could be detected,
thus demonstrating chiral sensing ability. It is worth mentioning
that this system oers great advantages for distinguishing chiral
metallosupramolecular complexes. For example, the authors
reported a three-way junction based on an E-DNA sensor. In this
study, the same palindromic DNA labeled with a redox-active
methylene blue (MB) tag at the 5-terminus was used as the
support. Discrimination of chiral metallosupramolecular complexes with an enantioselective recognition ratio of about 3.5 was
realized (Figure 129A and 129B).370 In another case, the authors
reported a similar electrochemical DNA (E-DNA) chiral sensor
based on the human telomeric G-quadruplex formation. An
enantioselective recognition on zinc-nger-like chiral metallosupramolecular assemblies reaches ratios higher than 5 (Figure
129C).371
As previously described, supramolecular chiral assemblies have
good capabilities for the recognition of low molecular weight
chiral organic molecules. Worthy of note are the chiral
supramolecular assemblies that can recognize very small amounts
of chiral molecules. In this context, we will show some
representative examples of chiral sensing based on supramolecular assemblies.
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Figure 128. (A) Molecular structures of the secondary terephthalamide derivatives containing four aryl blades (153) and their dierent conformations.
(B) Schematic image showing the conformational changes from a nonpropeller anti form to a propeller-shaped syn form upon forming complexes with
chiral guests. Reprinted with permission from ref 369. Copyright 2009 American Chemical Society.
Figure 129. (A) Schematic illustration of a three-way junction based on E-DNA for distinguishing chiral metallo-supramolecular complexes. (B)
Changes of current from the E-DNA sensor showing discrimination of chiral metallosupramolecular complexes. (C) Schematic representation of the
human telomeric DNA-based electrochemical DNA (E-DNA) sensor. Reprinted with permission from refs 370 and 371. Copyright 2012 The Royal
Society of Chemistry.
Figure 130. Self-assembly of zinc porphyrin dimers can lead to box-shaped tetramers, which shows chiroptical sensing for limonene. Reprinted with
permission from ref 372. Copyright 2007 John Wiley & Sons.
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Figure 131. (A) Four-component reversible covalent assembly for secondary alcohol binding. OTf is triuoromethanesulfonate (triate). (B)
Exploration of four-component assembly for chirality sensing and ee determination. CD spectra of 1-phenylethanol-induced assembly with dierent ees
of the alcohol (from top to bottom 100%, 80%, 60%, 40%, 20%, 0%, 20%, 40%, 60%, 80%, 100%). Reprinted with permission from ref 373.
Copyright 2011 Nature Publishing Group.
Figure 132. (A) Schematic illustration of the chiral sensing based on the
ternary complexes between the macrocyclic host cucurbit[8]uril,
dicationic dyes, and chiral aromatic analytes. (B) Examples of reaction
monitoring. Reprinted with permission from ref 374. Copyright 2014
John Wiley & Sons.
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Figure 133. Changes induced in the chiral plasmonic resonances of the planar chiral metamaterials (PCM) are readily detected using CD spectroscopy.
(A) CD spectra collected from PCMs immersed in distilled water. (B) Inuence of the adsorbed proteins hemoglobin, -lactoglobulin, and thermally
denatured -lactoglobulin on the CD spectra of the PCMs. (C) Hemoglobin (top) and -lactoglobulin (bottom) (-helix, cyan cylinder; -sheet,
ribbons), shown adopting a well-dened arbitrary structure with respect to a surface. The gure illustrates the more anisotropic nature of adsorbed lactoglobulin. Reprinted with permission from ref 381. Copyright 2010 Nature Publishing Group.
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The very good stimulus-responsive properties of selfassembled systems based on noncovalent interactions can help
these systems form chiral switches with unique performance. For
example, Liu et al. synthesized a glutamic-acid-based lipid
containing an azobenzene headgroup (azo-LG2C18, 5), which
can form organogels with supramolecular chirality in dierent
organic solvents. Remarkably, the resulting organogels can be
used as chiroptical switches with multiresponsibility. Thus, the
supramolecular chirality can be changed reversibly by photoirradiation, temperature variation, or solvent polarity (Figure
139).56
A supramolecular chiroptical switch based on multicomponent self-assembled soft matters has also been developed by Liu
group. The self-assembly of chiral glutamic-acid-based bolaamphiphiles (HDGA, 15b) can lead to hydrogels and chiral
supramolecular nanotubes. For the construction of multicomponent soft matters, the azobenzene derivative 4(phenylazo)benzoic acid sodium salt (Azo) can be coassembled
with either HDGA molecules (15b) or chiral supramolecular
nanotubes. Although very strong supramolecular chirality can be
detected from the coassembly of Azo with the preformed chiral
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Figure 140. (A) Structures of the hydrogelators HDGA (15b) and Azo. (B) Gels formed by L-HDGA in water in the absence and presence of Azo. (C)
Illustration of the coassembly of Azo with HDGA. Reprinted with permission from ref 404. Copyright 2011 The Royal Society of Chemistry.
well investigated, supramolecular polymers based on coordination interactions have very special characteristics for supramolecular chiral catalysis.
For example, Ding et al. constructed polymeric supramolecular chiral catalysts based on self-assembly. The authors
synthesized an organic ligand containing ureido-4[1H]ureidopyrimidone (UP) and Feringas MonoPhos motifs. By
mixing the organic ligand with [Rh(cod)2]BF4, supramolecular
polymers can be produced by orthogonal self-assembly via
hydrogen-bonding and ligand-to-metal coordination interactions. This supramolecular polymer shows excellent asymmetric
Figure 142. (A) Polymeric supramolecular chiral catalyst based on self-assembly. (B) Asymmetric hydrogenation of dehydro--amino acid and enamide
derivatives. Reprinted with permission from ref 423. Copyright 2006 John Wiley & Sons.
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Figure 143. (A) Molecular structure of a ligand containing the 2,2:6,2-terpyridine (tpy) unit and Feringas MonoPhos (160), and schematic
illustration of supramolecular catalysts through orthogonal coordination of two dierent metal ions with a single ditopic ligand. (B) Asymmetric
hydrogenation of dehydroamino acid, enamide, and itaconic acid derivatives using a catalyst with high reaction rate and excellent enantioselectivity.
Reprinted with permission from ref 424. Copyright 2010 John Wiley & Sons.
Figure 145. (A) Structures of chiral supramolecular catalyst (162). (B) Enantioselective DielsAlder reactions with anomalous endo/exo selectivities
using chiral supramolecular catalysts. Reprinted with permission from ref 426. Copyright 2011 John Wiley & Sons.
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Figure 147. Illustration of the assembly mechanism of the Cu2+LHDGA nanotubular structure and its asymmetric catalysis of the Diels
Alder reaction of aza-chalcone with cyclopentadiene. Reprinted with
permission from ref 428. Copyright 2011 American Chemical Society.
Besides catalytic nanotubes, chiral catalysis based on supramolecular nanostructures has also been observed using vesicles.
Liu et al. synthesized amphiphilic molecules containing a proline
headgroup (PTC12, 163). The self-assembly of PTC12 in water
under compressed CO2 can produce vesicles. These assemblies
were found to catalyze the asymmetric aldol reaction with high
enantiomeric selectivity without any additives. Importantly, the
size of the PTC12 assemblies and subsequently catalyst activity
and stereoselectivity can be dynamically modulated by changing
the status of the compressed CO2. Moreover, because CO2 can
be easily removed from the system, it is very convenient for the
separation and purication of products, as well as the reuse of the
chiral supramolecular catalysts (Figure 148).429
In the development of supramolecular chiral catalysis, chiral
covalent polymers, including some biomacromolecules, such as
DNA and polypeptides, can be used as building blocks. The
catalytic capability of these polymers may originate from the
molecular chiral centers within these polymers but may also
result from their folding characteristics and hierarchical
nanostructures.
Meijer and co-workers synthesized water-soluble segmented
terpolymers containing PEG and chiral benzene-1,3,5-tricarboxamide side chains as well as a ruthenium complex (164). Due to
the chiral self-assembly of the benzene-1,3,5-tricarboxamide side
chains, the folding of these polymers can produce a helical
structure in the apolar core around a ruthenium-based catalyst.
This catalyst, resulting from the folding of polymers, was found
to catalyze the transfer hydrogenation of ketones (Figure
149).430
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Figure 149. (A) Water-soluble segmented terpolymer containing PEG and chiral benzene-1,3,5-tricarboxamide side chains as well as a ruthenium
complex (164). (B) Supramolecular single-chain folding of polymers in water aording a compartmentalized catalyst for the transfer hydrogenation of
ketones. Reprinted with permission from ref 430. Copyright 2011 American Chemical Society.
Figure 150. Optically active polymers consisting of riboavin units catalyze the asymmetric organocatalytic oxidation of suldes. Reprinted with
permission from ref 431. Copyright 2012 American Chemical Society.
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Figure 151. (A) Asymmetric DielsAlder reaction of cyclopentadiene with aza-chalcone, catalyzed by copper complexes of the ligand in the presence of
DNA. (B) Asymmetric Michael addition reaction catalyzed by complexes formed between copper(II) ions and achiral ligands in the presence of DNA.
(C) Cudmbpy/st-DNA-catalyzed FriedelCrafts alkylation. Reprinted with permission from refs 432, 433, and434. Copyright 2005, 2007, and 2009
John Wiley & Sons. (D) DNA-based catalyst and general reaction scheme of the catalytic enantioselective hydration of a variety of ,-unsaturated 2acyl-(1-alkyl)imidazole substrates, and overview of ligands used in this study. Reprinted with permission from ref 436. Copyright 2010 Nature
Publishing Group. (E) Intramolecular cyclopropanation of -diazo--keto sulfones in water using a DNA-based catalyst. Reprinted with permission
from ref 435. Copyright 2013 The Royal Society of Chemistry.
Figure 152. Enantioselective DielsAlder reactions with G-quadruplex-DNA-based catalysts; the absolute conguration of the products can be reversed
when the conformation of the G4DNA is switched from antiparallel to parallel. Reprinted with permission from ref 438. Copyright 2012 John Wiley &
Sons.
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Figure 153. Tuning the absolute conguration in DNA-based asymmetric catalysis. Reprinted with permission from ref 439. Copyright 2013 John Wiley
& Sons.
Figure 154. Enantioselective cyclization of photochromic dithienylethenes bound to DNA. Reprinted with permission from ref 440.
Copyright 2013 John Wiley & Sons.
Figure 155. Enantioselective articial metalloenzymes based on a bovine pancreatic polypeptide scaold, showing catalytic DielsAlder and Michael
addition reactions in water with high enantioselectivities. Reprinted with permission from ref 441. Copyright 2009 John Wiley & Sons.
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Figure 159. Controllable fabrication of supramolecular nanocoils and nanoribbons and their morphology-dependent photoswitching. Reprinted with
permission from ref 455. Copyright 2009 American Chemical Society.
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Figure 164. SEM images of helical silica nanoribbons and silica twists;
adhesion and dierentiation of stem cells on helical silica nanoribbon
substrates. Reprinted with permission from ref 477. Copyright 2013
American Chemical Society.
Figure 165. Self-assembled nanostructures with opposite supramolecular chirality showing dierent adhesive ability to human serum
albumin. Reprinted with permission from ref 478. Copyright 2014
American Chemical Society.
AUTHOR INFORMATION
7. CONCLUSIONS
Chiral self-assembly from the molecular to the supramolecular
level represents one of the most attractive and promising areas in
supramolecular chemistry and self-assembly. The supramolecular chirality in these self-assembled systems is the expression of
the noncovalent interactions between the component molecules,
where chiral transfer from a chiral component to the whole
assembly plays an important role. In addition, supramolecular
chirality can also emerge through symmetry breaking even when
only achiral molecules are involved. Due to the dynamic features
of the self-assembly system, the supramolecular chirality can be
regulated through the design of the chiral molecules themselves,
external conditions such as pH, metal ions, photoirradiation,
solvents, temperature, sonication, and so on. Dierent from
molecular chirality, supramolecular chirality can exhibit unique
properties such as the sergeant-and-soldier principle, the
majority-rule principle, and chiral memories in several systems.
Supramolecular chirality in self-assembled systems has been
found to be useful in chiral sensing, chiral molecular recognition,
and asymmetric catalysis. Some new functions such as chiroptical
switching, chiroptics, and CPL have also been observed.
Furthermore, chiral nanostructures showed some interesting
properties when interacting with the biological systems. This
review has described many examples of the emergence,
regulation, and unique features or functions of the supramolecular chirality; however, there are still many unknowns
related to supramolecular chirality.
Corresponding Author
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REFERENCES
Tianyu Wang received his B.Sc. and M.Sc. degrees in Chemistry from
Tianjin University, China. He received his Ph.D. degree in Organic
Chemistry from the Institute of Chemistry of the Chinese Academy of
Sciences in 2001. After that he worked as a Postdoctoral Researcher at
the Free University of Berlin in Germany with Prof. Dr. J.-H. Fuhrhop.
Since 2007 he has been working as an Associate Professor at the Institute
of Chemistry, CAS. His research interests are supramolecular assemblies
and soft matters.
ACKNOWLEDGMENTS
This work was supported by the Basic Research Development
Program (2013CB834504), the National Natural Science
Foundation of China (Nos. and 21321063, 21473219,
21474118, and 91427302), and the Fund of the Chinese
Academy of Sciences (No. XDB12020200).
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