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Cite this: Chem. Soc. Rev., 2012, 41, 597–607

www.rsc.org/csr TUTORIAL REVIEW

Pillar[5]arenes: fascinating cyclophanes with a bright futurew
Peter J. Cragg* and Kushal Sharma
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Received 14th June 2011

DOI: 10.1039/c1cs15164a

Pillar[5]arenes are [15]paracyclophane derivatives consisting of 1,4-disubstituted hydroquinones

linked by methylene bridges in the 2,5-positions. The first report of these novel macrocycles was
in 2008, when 1,4-dimethoxypillar[5]arene was prepared in 22% yield, and subsequent
improvements in synthetic methods have allowed the number of derivatives to expand
significantly. In addition to D5 symmetric pillar[5]arenes, asymmetric pillar[5]arenes with two
different substituents in the 1- and 4-positions and copillar[5]arenes consisting of two different
repeat units in a 4 : 1 ratio have been synthesised. Crystallographic, computational and
spectroscopic studies are starting to shed light on the compounds’ unusual inclusion phenomena,
from gelation and transportation of water through nanotubes to the formation of chromogenic
rotaxanes. Applications as molecular sensors are starting to appear with a focus on guest
detection by fluorescence quenching. This tutorial review will provide a summary of research into
the pillar[5]arenes since their recent discovery.

Introduction Pellagrin in 18994 and cyclodextrins observed by Villiers in

It is rare that chemists can announce the arrival of a new class
of synthetic, functional macrocycles. Crown ethers date back
to Pedersen’s work in 19671 and phthalocyanines to the
discoveries made by Dandridge2 in the 1920’s. Cucurbiturils
were first prepared in 1905,3 metacyclophanes reported by
School of Pharmacy and Biomolecular Sciences, Huxley Building,
University of Brighton, Brighton BN2 4GJ, UK.
E-mail: P.J.Cragg@brighton.ac.uk; Fax: +44 1273 642647;
Tel: +44 1273 642037
w Electronic supplementary information (ESI) available: conforma-
tional analysis of pillar[5]arenes, through-the-annulus rotation
mechanisms and a note on cyclophane synthesis. See DOI: 10.1039/
c1cs15164a
1891.5 Calixarenes, resorcinarenes and calixpyrroles all date
back to Baeyer’s work on phenol-formaldehyde chemistry in
the 1870’s and 1880’s.6,7 It came as a surprise when, in 2008, a
new class of macrocycles, the pillar[n]arenes, appeared in the
literature.8 In the short time since their discovery the chemistry
of these fascinating macrocycles has developed rapidly with
new synthetic routes pursued, a wealth of inclusion pheno-
mena described, and the preparation of the first pillar[5]arene-
based molecular sensor. Their unusual symmetry has led
to some distinctive geometrical features and stereochemistry
with implications for their use in molecular recognition. This
tutorial review will provide a summary of research into the
cyclopentameric pillar[5]arenes.

Peter J. Cragg started his career
in macrocyclic chemistry as a
graduate student in the Atwood
group at the University of
Alabama. After a year as a post-
doctoral researcher at SUNY
Stony Brook, and a further
18 months at Reading Univer-
sity, he joined the University of
Brighton in 1993 where he is
currently Reader in Supramole-
cular and Bioinorganic Chemis-
try. His research interests
include biomimetic artificial ion
Peter J. Cragg channels, computational chemis-
try and macrocyclic synthesis.
Kushal Sharma received his BSc
(Hons) in Pharmaceutical and
Chemical Sciences from the
University of Brighton before
spending a year in industrial
formulation. In 2010 he started
postgraduate research in the
University of Brighton’s
Huxley Building laboratories
focusing on artificial ion
channels incorporating calix[4]-
arenes, oxacalix[3]arenes and
pillar[5]arenes.
Kushal Sharma

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 597–607 597

Structures, conformers and chirality
Pillar[n]arenes, named by Ogoshi and Nakamoto in their
2008 paper,8 are 1,4-disubstituted [1n]paracyclophanes derived
from hydroquinones linked by methylene bridges in the 2,5-
positions. In this they are structurally related to [15]paracyclo-
phane reported in 1985 by Gribble and Nutaitis.9 [1n]Para-
cyclophanes were prepared from linear precursors terminating
in a benzyl alcohol, as shown in Scheme 1. In the case of the
linear pentamer this involved 14 steps and an overall yield
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of 13% prior to cyclisation Macrocycles were successfully
prepared from the linear pentamer and hexamer, but not
the tetramer, with [16]paracyclophane isolated in 31% yield
and [15]paracyclophane in 10% yield. The final cyclisation
step occurred via a Friedel–Crafts reaction, unusual in that
most routes to [1n]paracyclophanes require that one of the
aromatic rings is formed following cyclisation of a less strained
precursor.10
An alternative convergent synthesis of [15]paracyclophane
was attempted, however, this gave an even lower yield in the
final step. The authors stated that:
‘‘the dismal yields obtained thus far in the final step preclude
a study of the p-complexing properties of [15]PCP and
[16]PCP’’9
Consequently the chemistry of these compounds was not
pursued further. Interestingly, the authors also noted that:
‘‘it is possible that Cannizzaro prepared [1n]PCPs as early
as 1854’’
If true, it would make [1n]paracyclophanes the first synthetic
macrocycles.w
Two other paracyclophanes deserve a mention here:
Osakada’s cyclic oligo(p-phenyleneoxide) compounds11 and
Ito’s N-anisyl hexaaza[16]paracyclophane12 (Fig. 1). Both have
the same paracyclophane structural motif but, in common
with the other examples given, have no functional groups on
the aromatic rings.
The pillar[n]arenes are distinct from these [1n]paracyclo-
phanes by virtue of having cleavable alkoxy groups in the 1,4-
positions making them amenable to further functionalisation in
Scheme 1 Synthesis of [15]paracyclophane.
598 Chem. Soc. Rev., 2012, 41, 597–607
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Fig. 1 Cyclic hexa(p-phenylene oxide) and N-anisyl-substituted
hexaaza[16]paracyclophane.
the manner of the calixarenes. Unlike calixarenes, formed from
4-substituted phenols linked in the 2,6-positions, pillar[n]arenes
are cylindrical rather than conical in shape and more
closely resemble the tubular geometry of the cucurbit[n]urils.
Importantly, and unlike most other phenol-based macrocycles,
pillar[n]arenes are readily functionalised on both upper and
lower rims. The structural similarities and differences between
these macrocycles are illustrated in Fig. 2.
A majority of papers concerned with pillar[n]arene synthesis
report the isolation of the cyclopentamer only. Cyclohexamers
have been prepared but always as minor products isolated in
approximately 10% yield.13 One reason for this is the degree of
bond angle strain across the methylene bridge. A cyclo-
tetramer would require an Ar–CH2–Ar bond angle of 901
whereas a cyclohexamer would need one of 1201. Crystallo-
graphic evidence shows that the average bond angle for the
methylene bridge in dimethoxypillar[5]arene (DMpillar[5]arene)
is 111.31, close to the ideal 109.51 angle for sp3 hybridised
carbons.8 It is also close to the ideal 1081 internal angle for an
unstrained pentagon. Consequently the cyclopentamer is the
main product from the macrocyclisation reactions.
The pillar[5]arenes have two interesting geometric
properties. Firstly, the presence of substituents in the 1- and
4-positions leads to two possible planar chiral stereoisomers,
Rp and Sp as shown in Fig. 3, that arise through the spatial
arrangement of the out of plane substituents. Secondly,
rotation of one or more of the aromatic rings through the
macrocyclic annulus generates conformational isomers. These
conformers can be likened to those available to the better
known calix[4]arenes. Fig. 4 illustrates the possible conformers
of Rp pillar[5]arene as identified by Ogoshi and Nakamoto:14
all rings in the same orientation, one ring inverted, two
adjacent rings inverted, and two non-adjacent rings inverted.
By analogy with calixarenes these can be described as cone,
partial cone, 1,2-alternate and 1,3-alternate, respectively.
The X-ray crystal structures of DMpillar[5]arene and
pillar[5]arene in Fig. 5 show that the former is isolated in the
D5 symmetric cone conformation, as a racemic mixture of Rp
and Sp enantiomers,8 whereas the latter has lost this symmetry.15
Two of the pillar[5]arene rings have become inverted with
respect to the remaining three to give the 1,3-alternate conformer
with C1 symmetry. This scrambling of the macrocycle appears
to have occurred to allow stabilising hydrogen bonds to form.
It would therefore seem likely that any attempt to extend the
pillar[5]arene cavity of such a low symmetry compound through
O-alkylation would generate a range of conformers,16 not to
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Fig. 2 Representative macrocycles: (from top) funnel-shaped calix[4]-
arene, planar phthalocyanine, tubular cucurbit[5]uril and DMpillar[5]-
arene.
Fig. 3 Planar chiral pillar[5]arenes: Sp (left) and Rp (right).
mention many more partially substituted compounds. As a
scaffold for further work it would make pillar[5]arene of little
interest as reproducible syntheses would be almost impossible to
design. Fortunately this is not the case as is explained below.
Synthesis of 1,4-dialklyated pillar[5]arenes
The simplest synthesis of 1,4-disubstituted pillar[5]arenes is
through cyclisation of the monomer with paraformaldehyde in
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Fig. 4 Pillar[5]arene conformers: (clockwise from top left) cone,
partial cone, 1,2-alternate, 1,3-alternate.
Fig. 5 X-Ray structures of DMpillar[5]arene and pillar[5]arene
(solvents removed for clarity).
the presence of a suitable catalyst. Other routes involve
cyclisation of 2,5-substituted derivatives of 1,4-dialkoxy-
benzne and O-alkylation of unsubstituted pillar[5]arene.
Direct cyclisation of 1,4-disubstituted benzene
1,4-Dimethoxypillar[5]arene (DMpillar[5]arene) was first
synthesised through the addition of a Lewis acid to 1,4-
dimethoxybenzene and paraformaldehyde in 1,2-dichloro-
ethane (Scheme 2).8 Several candidate Lewis acids were
tested, including H2SO4, FeCl3, AlCl3, TiCl4 and SnCl4, but
BF3OEt2 gave the cleanest yield of the macrocycle. A 1 : 1 ratio
of reagents was used, together with an equimolar quantity
of the Lewis acid, and the reaction undertaken at room
temperature. Gel permeation chromatography indicated that
the optimum reaction time was over three hours. The product
was isolated as a precipitate which formed when the reac-
tion mixture was poured into methanol. Recrystallisation
from CH3CN gave the product in 22% yield and X-ray
Scheme 2 Ogoshi’s synthesis of dimethoxypillar[5]arene.
Chem. Soc. Rev., 2012, 41, 597–607 599
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crystallography revealed that two solvent molecules remained

inside the macrocyclic cavity in the solid state. The crystal
structure also confirmed DMpillar[5]arene to be the cyclic
pentamer. As with many other phenol-formaldehyde based
macrocycles, through-the-annulus rotation was observed.
DMpillar[5]arene rotation appears fast on the NMR timescale
Scheme 3 Cao and Meier’s synthetic approach to 1,4-dialkoxypillar[5]-
giving rise to a series of singlets in the 1H NMR, at 6.84 ppm
arenes (R = Bz, Me, n-Bu, Et, H).
(ArH), 3.76 ppm (–CH2–) and 3.71 ppm (–CH3) in CDCl3, in
the ratio of 1 : 1 : 3 with no change in signal even at !90 1C.
higher homologues are formed by other routes but not
Ogoshi and Nakamoto have since shown that alkyl
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isolated.
substituted pillar[5]arenes can be prepared by the same general
Using a similar approach Huang reported that reaction of
method to give ethoxy, n-propoxy, n-butoxy, n-pentyloxy,
1,4-diisobutoxybenzene with paraformaldehyde and HBr in
n-hexyloxy or n-dodecanoxy groups in the 1,4-positions. The
glacial acetic acid led to the formation of the bis(bromomethyl)
yields of these derivatives varied from 7 to 28%.17
derivative. Following treatment with sodium methoxide the
Ogoshi also used this method to prepare pillar[5]arenes from
resulting di(methoxymethyl) derivatives were cyclised in refluxing
1,4-bis[2(S)-methylbutoxy)benzene and a racemic mixture of
CH2Cl2, with stoichiometric 4-toluenesulfonic acid hydrate, to
the R and S enantiomers, achieving yields of 10% and 67%,
give diisobutoxypillar[5]- and [6]arene with yields of 73% and
respectively.18 The compounds were subsequently used to
5%, respectively.20 As the first two steps are essentially quanti-
investigate the planar chirality of the pillar[5]arenes.
tative the method is an attractive alternative to direct cyclisation
In a later paper, variation in the ratio of 1,4-dimethoxy-
of 1,4-dialkoxybenzene precursors, especially when bulky sub-
benzene to paraformaldehyde was investigated and a value of
stituents are involved (Scheme 4).
1 : 3 found to give DMpillar[5]arene in an improved yield of
71%.15 While this can be achieved in 3 min, optimum condi-
tions for the reaction were determined to be 30 1C for 30 min. Asymmetric pillar[5]arenes
The reaction is deceptively simple: 1,4-dimethoxybenzene is Asymmetric pillar[5]arenes, such as 1-ethoxy-4-methoxypillar[5]-
first dissolved in dichloroethane then paraformaldehyde is arene (EMpillar[5]arene), can be prepared through cyclisation of
added. The reaction mixture is stirred rapidly under nitrogen asymmetric precursors using Ogoshi’s method. Extensive NMR
before BF3OEt2 is added in a single portion. There is an studies carried out by Ogoshi and Nakamoto21 and Huang16 on
immediate change from colourless to an intense blue-green the asymmetric EMpillar[5]arene, synthesised from 1-ethoxy-4-
colour. It appears that temperature is critical as much above methoxybenzene, showed that rotation through the annulus was
30 1C an intractable dimethoxybenzene-formaldehyde poly- too slow on the variable temperature NMR timescale to be
mer is formed. Despite this, the method is attractive due to the observed. Initially, Ogoshi reported 2D ROESY data which
low cost of starting materials and the ability to significantly indicated that in solution the product was in a single form with
scale up the reaction. Upon completion the reaction mixture is all the methoxy groups coplanar and the ethoxy groups on the
poured into methanol whereupon an off-white solid precipi- opposite face rather than the expected statistical distribution
tates. The fine powder can be recrystallised from either of conformers. 1H NMR in DMSO-d6 showed that signals
CH3CN or CHCl3/acetone (1 : 1 v/v) to give a white, micro- due to the methylene bridges were split even at 110 1C whereas
crystalline solid. signals from the methyl and ethyl substituents, although
initially split, coalesced into singlets above 110 1C. A swinging
Cyclisation of 1,4-disubstituted-2,5-dimethoxymethybenzene motion of the aromatic moieties, by which they rock in and
and other derivatives out of the central cavity, was invoked as the reason for the
changes in multiplicity. Huang reported the crystal structure
Following the publication of the initial low yielding synthesis of EMpillar[5]arene (in his ESI16) which serves to illustrate the
of DMpillar[5]arene in 2008 the race was on to find an
improved route. Cao and Meier reported that refluxing
2,5-bis(benzyloxymethyl)-1,4-diethoxybenzene in CH2Cl2
containing catalytic 4-toluenesulfonic acid gave the corres-
ponding diethoxypillar[5]arene in 75% yield (Scheme 3).19 The
2,5-bis(ethoxymethyl) analogue was even more efficient giving
a 92% yield and other ethers were similarly effective. This
route was also used to prepare DMpillar[5]arene and di-n-
butylpillar[5]arene. In all cases macrocycles were formed
almost quantitatively by this method and column chromato-
graphy (petroleum ether/ethyl acetate, 40 : 1 v/v, on silica) was
used to separate the pillar[5]arenes from their pillar[6]arene
homologues.
This was the first method to generate pillar[6]arenes, however,
as residues from other routes were assumed to be unwanted Scheme 4 Huang’s general three step synthesis of 1,4-dialkoxypillar[5]-
polymers and not investigated further it may transpire that arenes.

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 View Article Online

similarities between the conformers’ properties. Despite isola-
tion by chromatography and displaying a single spot by TLC,
the unit cell of the crystalline compound contained two
dissimilar molecules; one a partial cone conformer and the
other a 1,3-alternate conformer.
Another asymmetric pillar[5]arene, BMpillar[5]arene,
formed from 1-butoxy-4-methoxybenzene, was reported both
by Cao and Meier19 and Huang.16 Unlike the less bulky
EMpillar[5]arene, BMpillar[5]arene gave four spots by TLC,
each one corresponding to one of the possible conformers,
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has C1 symmetry subsequent O-alkylation generates a D5 sym-
metric product exclusively which makes product isolation and
purification relatively simple.
Ogoshi and Nakamoto have shown that reaction with
bromoethylacetate followed by cleavage of the ester with
NaH and addition of NH3, as in Scheme 6, yields a water
soluble pillar[5]arene.22 Given the poor solubility of
pillar[5]arenes in general this is an important development
analogous to the synthesis of the water-soluble sulfonate
derivatives in the calixarene field.23 An alternative route,

which could be separated by chromatography and crystallised reported by Hou, can be used to prepare an amine derivative
from CH3CN19 or n-hexane.16 Huang has systematically (Scheme 6). Reduction of the acetate to the alcohol with
shown that, building up from the monomer to the cyclic LiAlH4 followed by bromination with CBr4 gave the
pentamers, there are only two routes to the cone conformer, deca(ethylbromide). Treatment with NaN3 followed by hydro-
one of which is in the Rp form and one in the Sp. The same genation in the presence of Pd/C gave the desired decaamine in
analysis shows that there are 10 routes to each of the partial an impressive 33% yield from the pillar[5]arene parent.24
cone, 1,2-alternate and 1,3-alternate conformers, half of which Ogoshi and Nakamoto synthesised pillar[5]arenes with
give rise to Rp and the other half the Sp forms. This gives a bulky methyl- and ethylcyclohexane substituents to demon-
theoretical conformer distribution of 1 : 5 : 5 : 5 which was strate that the Rp and Sp forms could be separated by HPLC
closely matched experimentally by both groups.16 using a chiral column.25 As the first proof of planar chirality
this represented a valuable application of this synthetic
approach.
Pillar[5]arene and its reactions
An alternative to cyclising appropriately 1,4-disubstituted
hydroquinone derivatives is to start from DMpillar[5]arene
and remove the methyl groups. Pillar[5]arene is readily
obtained from DMpillar[5]arene by the action of BBr3 in
CHCl3 over three days as shown in Scheme 5. Initially the
conversion was found to be 30%8 but when anhydrous chloro-
form was used this became quantitative.15 The 1H NMR for
the compound in acetone-d6 is very simple comprising singlets
at 7.96 ppm (–OH), 6.66 ppm (ArH) and 3.59 ppm (–CH2–)
in the expected 1 : 1 : 1 ratio. This indicates that, although the
1,3-alternate conformer crystallises preferentially, pillar[5]arene
remains fluxional in solution. Pillar[5]arene is consequently a
valuable starting material from which the macrocyclic frame-
work can be extended by various means, notably by reaction
with alkyl halides. Pillar[5]arene has greatly improved solubility
over its dimethoxy derivative in CH3OH, CH3CN, acetone,
DMF and DMSO which opens up a potentially vast range of
reaction conditions.
Reaction of pillar[5]arene with an alkylating agent in the
presence of a suitable base is the simplest route to extended
pillar[5]arenes. This would appear unlikely to succeed as the
steric crowding around the macrocyclic annulus should work
against complete decasubstitution. Nevertheless, deprotona-
tion with NaH followed by the addition of excess alkyl halide
has successfully produced numerous pillar[5]arenes containing
a range of substituents, from alkyl chains and cyclohexyl
groups to esters and polyethers, many of which are amenable
to further functionalisation. Although crystalline pillar[5]arene

Scheme 5 Synthesis of pillar[5]arene. Scheme 6 Carboxylate and alkylamine pillar[5]arene derivatives.

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Surprisingly bulky groups can be introduced by this method.

Reaction of the pillar[5]arene sodium salt with an excess of
propargyl bromide gives the decasubstituted derivative in 66%
yield after workup.26 This derivative is amenable to high
yielding ‘click’ chemistry which has been employed to synthesise
the n-hexyl, benzyl and pyrenyl derivatives in 63%, 20% and
9% yield, respectively. There is a clear link between yield and
steric bulk of the substituents, nevertheless, the fact that ten
pyrenyl groups can be attached to pillar[5]arene is an impressive
feat in itself.
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Pillar[5]arene also reacts with trifluoromethane sulfonic

anhydride, as reported by Ogoshi and Nakamoto, to give
the decatriflate. Sonogashira coupling with ethynylbenzene
in the presence of a palladium catalyst yields a fluorescent
derivative, DPhEpillar[5]arene, shown in Scheme 7.27 The
extended p-surface would seem to make this pillar[5]arene an
ideal host for electron deficient and cationic guests by analogy
to 1,3-alternate calix[4]arenes.28
Some further reactions of O-alkylated pillar[5]arenes
are illustrated in Scheme 8. The first is the oxidation of
DEpillar[5]arene by Cao and Meier who used (NH4)2-
[Ce(NO3)6] to prepare pillar[5]quinone in 62% yield.13 The
authors noted that it represented the first synthesis of a
cyclic quinone and drew parallels with the structure of
cucurbit[5]uril. Two other reactions relate to the decomposi-
tion of DMpillar[5]arene. Cao reported that reaction of the
macrocycle with N-bromosuccinamide in acetone, rather than
brominating the methyl groups, cleaves the macrocycle to give
bis(4-bromo-2,5-dimethoxyphenyl)methane. Similarly, the
action of 49% nitric acid does not generate the nitrated
pillar[5]arene but the nitrated decomposition product, bis-
Scheme 8 Reactions of O-alkylated pillar[5]arenes: pillar[5]quinone
(4-nitro-2,5-dimethoxyphenyl)methane.29 These last two reac- synthesis and macrocycle cleavage.
tions reveal that the pillar[5]arenes are perhaps not as robust
as other phenolic macrocycles; calix[n]arenes readily react with
nitric acid and other reagents without decomposition. in 16% yield. X-Ray crystallography showed the compounds
to have all the aromatic rings in the pseudo D5 orientation.
Copillar[5]arenes Despite the apparently greater problems of steric crowding
interfering with its synthesis, the copillar[5]arene formed
In addition to asymmetric pillar[5]arenes it has been shown by through the 4 : 1 reaction between 1,4-dimethoxybenzene
Huang that a copillar[5]arene is formed by combining one and 1,4-di-n-octyloxybenzene gives a much higher yield of
equivalent of 1,4-dimethoxybenzene with four of 1,4-di-n- 27%. Huang also prepared a copillar[5]arene based on
butyloxybenzene, albeit in less than 10% yield.30 The 4 : 1 DMpillar[5]arene in which one 1,4-dimethoxybenzene group
mixture also forms a copillar[5]arene, this time containing four is substituted with 1-methoxy-4-(octyloxy)benzene.31 The
dimethoxybenzene groups and one di-n-butoxybenzene group, modest yield of 9% was worth the work as the compound
was able to form supramolecular polymers, discussed below.
An alternative route to copillar[5]arenes directly from
DMpillar[5]arene has been identified by Ogoshi.32 In papers
on the synthesis of pillar[5]arene it was noted that when a trace
of water was present in the CHCl3:
‘‘the reaction mixture became cloudy during the reaction,
indicating the presence of partially deprotected pillar[5]arene’’15
This observation led the group to experiment with shorter
reaction times in order to isolate the monodeprotected pillar[5]-
arene. Deprotection conditions used anhydrous CHCl3, as
before, but only 0.9 equivalents of BBr3 were added and the
reaction mixture was poured into water after 45 min. Addition
of the organic phase to methanol precipitated a mixture of
starting material and the target compound which was purified
Scheme 7 Extending pillar[5]arenes by Sonogashira coupling. by column chromatography (CHCl3 : acetone 18 : 1 v/v on silica)

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to give pure monodeprotected DMpillar[5]arene in 22%

yield. Subsequent reaction with NaH and an excess of
N-(8-bromooctyl)trimethylammonium hexafluorophosphate
gave the monosubstituted copillar[5]arene in 49% yield after
workup. In acetone-d6 the alkylammonium methyl groups
appeared at 3.3 ppm, the same position as found for the free
trimethylammonium salt, whereas in CDCl3 there is a shift to
2.4 ppm indicating self-inclusion of the trimethyl group into
the macrocyclic cavity.
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X-Ray structures and what they reveal

Despite the limited solubility of most pillar[5]arene derivatives
it is fortunate that when they can be isolated from solution it is
in the form of robust crystals. X-Ray crystallography has been
invaluable in confirming conformational assumptions made
on the basis of NMR data. For example, the regular D5
structure of DMpillar[5]arene and that of pillar[5]arene,
where there is some ring inversion, could only be verified from
the crystal structures themselves. Other information of interest
to macrocyclic chemists can also be gleaned from crystallo-
graphic data, notably the dimensions of the pillar[5]arenes.
The rigid central cavity is approximately 5.5 Å across, large
enough to accommodate solvents such as CH3CN or hexane,
and anywhere from 6.5 Å deep, for pillar[5]arene, to 18 Å
deep, for a diethylacetato derivative.33 DMpillar[5]arene has Fig. 6 X-Ray structures of asymmetric pillar[5]arene constitutional
isomers: (clockwise from top left) cone, partial cone, 1,2-alternate,
external dimensions of 13 Å across by 13 Å deep and it may be
1,3-alternate (solvents and hydrogen atoms removed for clarity).
that this regular shape is partly responsible for its much lower
solubility when compared to most other pillar[5]arene deriva-
threaded through the annulus, a phenomenon that will be seen to
tives. Analysis of the all the pillar[5]arene crystal structures so
have implications for molecular recognition, as discussed later.
far published also shows that, while Rp or Sp enantiomers are
Even more interestingly, the macrocycles were in a pseudo D5
found in the asymmetric units, racemic mixtures are found in
form as shown in Fig. 7.
the unit cells due to the presence of crystallographic inversion
Huang’s copillar[5]arene comprising one 1-methoxy-4-
centres.
(octyloxy)benzene and four 1,4-dimethoxybenzene groups
The correlation between 2D 1H NMR and conformation of
can be pulled into regular rod-like nanofibres from concen-
asymmetric pillar[5]arene derivatives can be proven through
trated CHCl3 solution, which were shown by SEM to have a
the chromatographic separation and crystallisation of confor-
diameter of 9.5 mm.31 Single crystals were then grown from
mers followed by X-ray diffraction and NMR experiments on
CHCl3/CH3OH with the assumption that solvent had been
each isolated species. To illustrate this all four conformers of
included within the macrocyclic cavity. Crystallography
1-butoxy-4-methoxypillar[5]arene are shown in Fig. 6.
revealed that the n-octyl substituent of one molecule threaded
The crystal structures of these compounds were reported
through the annulus of the next so that each macrocycle was
independently by Meier19 and Huang.16 All of Meier’s
threaded onto its neighbour, as seen in Fig. 8, resulting in a
compounds crystallized with CH3CN in the central cavity
unidirectional stack of pillar[5]arenes.
but only one of Huang’s compounds, the cone conformer,
was isolated as the hexane inclusion complex. This would seem
to indicate that pillar[5]arenes are quite catholic in their choice
of guests although, as will be seen later, they are able to
discriminate in favour of alkyl diamines.
As noted above, one of the more surprising discoveries
has been that reactions involving a 4 : 1 ratio of two different
1,4-dialkoxybenzene precursors yield pillar[5]arenes incorporating
the two different subunits in a 4 : 1 ratio.30 X-Ray crystallography
has demonstrated that the 4 : 1 copillar[5]arenes, isolable by
crystallisation from CH2Cl2 or hexane, do indeed have the
proposed 4 : 1 constitution as indicated by spectroscopy and
spectrometry. When CH2Cl2 was used as a solvent, the molecules
were situated at the macrocyclic mouths and noticeable inter-
actions existed between the aromatic rings and both hydrogen Fig. 7 X-Ray structure of a 4 : 1 copillar[5]arene prepared from
and chlorine atoms of the solvent. Conversely, hexane was found 1,4-dimethoxybenzene and 1,4-dibutyloxybenzene.

This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 597–607 603

Fig. 8 An interpenetrating copillar[5]arene structural motif.
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As these aggregates were not found at low concentrations it
was argued that reversible self-including monomers, mutually
including dimers or cyclic interpenetrating oligomers must
exist under these conditions. However, at higher concen-
trations (above 275 mM) linear supramolecular polymers
predominated.
Diethylacetatopillar[5]arene forms several solid state
structures, including xerogels when added to a 2 : 1 mixture
of CH2Cl2 : ethyl acetate, reported by Chen and Hou.33 Some
of these show the central cavity to be filled with eight hydrogen
bonded water molecules (Fig. 9) in a linear fashion. Hydrogen
bonding is presumed by the 2.6 Å spacing between adjacent
oxygen atoms which compares favourably with the predicted
behaviour of hydrogen bonded water chains within nano-
tubes.34 These ‘water wires’ exhibited selective proton
conductance as evidenced by soaking the crystals in D2O for
a week. After treatment the crystals had identical unit cell
dimensions but infrared spectroscopy revealed that O–D
stretches were present, indicating that deuterium had replaced
hydrogen in the solvent wires. As the analogous soaking
experiment with H218O failed to show incorporation of 18O,
the presence of deuterium had to be due to D+/H+ exchange
and a subsequent ‘proton hopping’ mechanism by D+.
Rotational freedom and inclusion phenomema
As outlined above, reaction of pillar[5]arene with 1-bromo-2-
cyclohexylethane25 or ethyl bromoacetate22 returned the
asymmetric macrocycle to the pseudo D5 symmetric form as
shown by X-ray crystallography of the former and 1H–1H
COSY NMR spectra of the latter. To understand why this
happens it is first necessary to determine the steric implications
of the conformers available to disubstituted and unsubstituted
pillar[5]arenes. Consideration of DMpillar[5]arene indicates
Fig. 9 X-Ray structure of DEApillar[5]arene showing packing (top)
and water filled channels (bottom).
604 Chem. Soc. Rev., 2012, 41, 597–607
View Article Online
that unfavourable interactions between methyl groups render
the D5 cone conformer most likely to represent the most stable
structure. Examination of the pillar[5]arene X-ray crystal
structure reveals a hydrogen bonding network involving eight
phenolic oxygens and four hydrogens. DMpillar[5]arene there-
fore adopts the D5 cone conformer due to steric constraints
and pillar[5]arene adopts the less symmetric 1,3-alternate
conformer through the stabilising influence of hydrogen
bonds.w
Once pillar[5]arene is deprotonated the resulting anions
react with approaching alky halide molecules. The steric bulk
of the resulting O-alkylated aromatic moieties forces a return
to the symmetric and sterically less demanding D5 cone
conformer. Ogoshi claimed that O-alkylation occurred with-
out inversion of planar chirality and was supported by 1H
NMR data and crystal structures.25 Once DMpillar[5]arene
has been demethylated only two rings need to rotate for
pillar[5]arene to adopt its most stable hydrogen bonded
conformer. The lowest energy pathway by which pillar[5]-
arene can revert to the D5 cone conformer following
O-alkylation will therefore be to rotate back to its original
Rp or Sp enantiomer rather than to rotate three more rings
leading to an inversion of planar chirality. It is this simple
twist of fate that makes pillar[5]arene derivatives so accessible.
Rotational freedom of pillar[5]arenes, by analogy with the
calixarenes, has been studied, usually indirectly through the
broadening of host NMR signals upon guest binding, with
a view to determining guest selectivity. For example,
DMpillar[5]arene methylene protons exhibit singlets in the
1
H NMR indicating that there is no barrier to through-the
annulus-rotation; the fact that these signals are split for
EMpillar[5]arene suggests strongly that rotation is inhibited
for substituents larger than methoxy groups.w 1H NMR
investigation of 1,4-dialkoxypillar[5]arenes by Ogoshi and
Nakamoto17 supports this assertion. As with the asymmetric
EMpillar[5]arene discussed earlier, a swinging motion was
invoked to explain coalescence of signals arising from the
hydrogens on the a-carbons. At low temperatures one set of
methylene hydrogens was presumed to be over the annulus
while those in the para-position resided outside. As the
temperature increased, these two sets of signals became
equivalent on the NMR timescale and, as expected, coales-
cence temperatures increased with increasing lengths of alkoxy
substituents, from !41 1C for the ethoxy derivatives to 39 1C
for the dodecyl derivatives. By comparison, the proton NMR
signals for the methylene bridge of the unsubstituted
pillar[5]arene coalesce at !60 1C. DMpillar[5]arene has no
hydrogen bonds to make or break so its rotation is hindered
only by interactions between methyl groups as they pass
through the annulus. Pillar[5]arene must break its hydrogen
bond network in order for the aromatic rings to rotate so its
rotation is slower on the NMR timescale. Subsequent addition
of a viologen guest to pillar[5]arene slows rotation at !30 1C
and when the temperature drops to !60 1C the macrocycle is
effectively frozen into one stable conformer.13
Pillar[5]arene derivatives from 1,4-bis[2(S)-methylbutoxy)-
benzene and a racemic mixture of R and S enantiomers were
used to probe interconversion between the two planar chiral
forms. As a solution of the racemic derivative was cooled the
This journal is c The Royal Society of Chemistry 2012

two enantiomers could be detected by circular dichroism and
variable temperature 1H NMR.18 As expected, racemisation
was fastest in high permitivity solvents, such as acetone, and
when the solution was heated. Cooling, use of low permitivity
solvents, or addition of guests, such as octyltrimethyl ammo-
nium hexafluorophosphate, slowed the rate of racemisation.
Similar effects were observed for DMpillar[5]arene which has
aromatic moieties that can rotate through the annulus to
switch between Rp and Sp forms. Conversion between the
two was again observed through changes in circular dichroism
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intensities.
Host–guest inclusion complexes were always going to be
important aspects of the chemistry of pillar[5]arene deriva-
tives. As with other macrocycles, pillar[5]arenes can be used as
molecular ‘beads’ and threaded onto a ‘string’ composed of
linked viologens as discussed in Ogoshi and Nakamoto’s
original paper as well as many more recent reports.8,14,35,36
The first report of pillar[5]arene inclusion behaviour used 1H
NMR to investigate the degree to which host–guest inter-
actions were present. In acetone-d6 the pyridinium and
a-methylene proton signals of octylpyridinium hexafluoro-
phosphate exhibited large upfield shifts, approaching 1 ppm,
indicating that the pyridinium group was held within the
pillar[5]arene annulus. Only the pyridinum proton signals
in the analogous di(octyl)viologen salt were shifted which
indicated that the octyl substituents were external to the
macrocyclic cavity. Complexation was verified by MALDI-
TOF mass spectrometry which gave signals for the doubly
charged complex. When a di(adamantyl)viologen salt was
added to pillar[5]arene no changes in spectra were observed
as the adamantyl groups were too large to enter the macro-
cycle’s cavity.
Rotaxanes can be prepared using a similar method whereby
a polymer comprised of viologen groups linked by propyl or
octyl chains can be used as ‘threads’ for pillar[5]arene. The
pseudorotaxane formed in this manner35 can be capped with
adamantyl groups as the hydrogen bonding network between
adjacent pillar[5]arenes holds the ‘beads’ together.36 The
resulting [3]rotaxane contains three pillar[5]arene shuttles
and is yellow in DMSO but turns violet upon heating. The
thermally induced colour change is a result of weakened
hydrogen bonds which allows the pillar[5]arenes to shuttle
rapidly along the rotaxane axis, transferring electrons from the
shuttles to the viologen groups, and stabilising a radical
cationic species. Examples of these inclusion complexes are
shown in Fig. 10.
Other quaternarised nitrogen-containing aromatic systems
can also act as molecular ‘threads’.37 Alkyl substituted para-
quats form pseudo[2]rotaxanes and even 1,4-bis(pyridinium)-
butane forms a stable 1 : 1 complex with an association
constant in the region of 103 M!1. The closely related
1,4-bis[N-(N 0 -hydroimidazolium)]butane ‘thread’ forms a
similar pseudo[2]rotaxane under pH control.38 This affinity
for charged species has been extended to ionic liquids, speci-
fically 1-hexyl-3-methylimidazolium bromide, which forms a
stable 1 : 1 complex with pillar[5]arene.39
The rotaxanes and pseudorotaxanes formed by pillar[5]-
arenes are reminiscent of similar supramolecules formed with
cucurbituril40 and cyclodextrin41 shuttles but the aromatic
This journal is c The Royal Society of Chemistry 2012
View Article Online
Fig. 10 Inclusion complexes and rotaxanes formed from pillar[5]-
arene derivatives.
repeat pattern found in the pillar[5]arenes is much more
amenable to the complementary interactions between shuttles
and aromatic ‘stations’ seen in Stoddart’s benzocrown ether
catenanes.42 Consequently there should be an interesting
future for pillar[5]arene rotaxanes with the potential for them
to find applications as ‘on/off’ states in molecular computers.
To date there has been no investigation of the simple
coordination or inclusion chemistry of the pillar[5]arenes
although Lau and Yu have undertaken a computational study
of pillar[n]quinones (n = 3–7) to investigate both tube forma-
tion and anion binding.43 Calculations using density func-
tional theory predicted that the pillar[5]quinone was the most
stable of the compounds investigated, though the cyclo-
tetramer, cyclohexamer and cycloheptamer were also likely
to be stable, and that both pillar[5]- and [7]quinones should
form tubular dimers. It was also determined that pillar[5]-
quinone should form stable complexes with both Cl! and Br!
with the former being marginally more stable (Fig. 11).
Complexation required little structural rearrangement but
would involve significant anion-p interactions. If experi-
mentally verifiable, the predicted Cl! binding by pillar[5]quinone
may have important biomimetic consequences as it has been
proposed that the hydrophobic central pore of transmembrane
COMP proteins formed by five interlocking polypeptide strands
may act as Cl! channels.44
Applications
In the first example of a pillar[5]arene-based sensor, Stoddart
reported a fluorescent copillar[5]arene that is quenched when
binding alkanediamines.45 The inspiration for this derivative
came from the realisation that alkyldiamines were bound by
DMpillar[5]arene and that this affinity could be exploited if the
binding event could be reported. Initial experiments deter-
mined that DMpillar[5]arene could form pseudorotaxanes
with 1,8-diaminooctane: significant upfield shifts were seen
in the 1H NMR for all hydrogens in the molecule’s alkyl
backbone. Similar, though weaker, effects were observed for
Chem. Soc. Rev., 2012, 41, 597–607 605
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Fig. 11 Pillar[5]quinone complexes of Cl! (left) and Br! (right).
n-octylamine. Further proof of diamine inclusion came
through the synthesis of a [2]rotaxane from the 1,8-diamino-
octane complex. The pseudorotaxane was treated with 3,5-di-
t-butylbenzaldehyde and reduced with NaBH4. The 1H NMR
spectrum of the rotaxane thread gave even more significant
shifts; the hydrogens furthest from the rotaxane caps, and
presumable those held most strongly within the DMpillar[5]-
arene shuttle, appeared at !1.2 ppm rather than 1.55 ppm.
Translation of these effects into a sensor was achieved using
the classical ‘receptor-spacer-reporter’ motif encountered in
many multifunctional or supramolecular sensors. Here the
macrocyclic cavity was the receptor and a pyrene fluorophore
gave the response. As Stoddart rightly states:
‘‘Monofunctionalization of macrocycles is a known strategy
for incorporating sensor capabilities without significantly
altering the binding ability of the host.’’45
The parent copillar[5]arene, shown in Scheme 9, was
prepared from a 4 : 1 ratio of dimethoxybenzene and 1-(2-
bromoethoxy)-4-methoxybenzene. Reaction with NaN3 followed
by a copper catalysed ‘click’ reaction with 1-(propargyl-
oxymethyl)pyrene gave the fluorescent monofunctionalised
copillar[5]arene in an overall yield of 7%. The compound was
soluble in CH3CN/H2O (1 : 1 v/v) which allowed the forma-
tion of pseudorotaxanes with alkylamines and diamines to be
followed by fluorescence quenching at 395 nm. Association
constants were generally higher for a,o-alkyldiamines than for
n-alkylamines although significant responses were also seen for
the key biogenic polyamines, spermidine and spermine.
Ogoshi subsequently prepared a pyrenyl derivative26 that
exhibited both monomer and excimer fluorescence, however,
the excimers are temperature dependent. Excimers form at
lower temperatures when the rocking mode of the pillar[5]-
arene’s aromatic moieties is at its slowest. As the temperature
increases from 20 1C to 80 1C the excimer emission intensity is
reduced by over 50% whereas the weak monomer emissions
are largely unaffected. The authors suggest that pillar[5]arene
fluorescence could be used to monitor guest binding as is
currently the case with numerous calixarene derivatives.46
Summary and outlook
Pillar[5]arenes are a new class of cyclophanes with similarities
to the better known calix[n]arenes. Unlike the calix[n]arenes
and many other macrocycles, the pillar[5]arenes are tubular
rather than funnel shaped compounds. The first pillar[5]arene,
a dimethoxy derivative with D5 symmetry, was found to be
poorly soluble in most solvents, and insoluble in water,
606 Chem. Soc. Rev., 2012, 41, 597–607
View Article Online
Scheme 9 Stoddart’s synthesis of a fluorescent copillar[5]arene.
however, removal of the methyl groups gave pillar[5]arene
which had improved the non-aqueous solubility. Pillar[5]arene
is amenable to substitution at all ten phenolic sites following
addition of base and a suitable alkylating agent with
further functionalisation possible through ‘click’ chemistry.
Although pillar[5]arene is asymmetric due to the formation of
four stabilising hydrogen bonds, reaction with alkyl halides
regenerates the D5 symmetry as a consequence of unfavour-
able steric interactions. A variety of pillar[5]arene derivatives
have been prepared and shown to have unusual properties.
Reaction with bromoethylacetate yields a compound that
forms water filled nanotubes; subsequent cleavage of the ester
and addition of ammonia leads to the formation of a water-
soluble derivative. Asymmetric pillar[5]arenes can be prepared
from asymmetric hydroquinone precursors and copillar[5]-
arenes form from 4 : 1 mixtures of two different precursors.
Monodeprotection also gives access to copillar[5]arenes
through reaction at the free phenolic site. The host–guest
chemistry of the pillar[5]arenes ranges from binding simple
solvents to viologens and other quaternary amines leading to
several different inclusion, and self inclusion, motifs including
rotaxane and pseudorotaxane formation.
Following the initial discovery of these unusually symmetric
macrocycles, attention turned to the introduction of substitu-
ents that could improve functionality. One approach is to
include fluorophores that report the inclusion of guest mole-
cules. Other methods of signalling pillar[5]arene complex
formation are bound to follow using the same approaches as
those so effectively pioneered with other phenolic macrocycles
such as the calixarenes. However, to be fully effective there
needs to be greater discrimination between guests; fortunately
research is being actively pursued on this front.
This journal is c The Royal Society of Chemistry 2012

The chemistry of pillar[5]arenes, and their higher homo-
logues, has only just started to be uncovered, yet despite their
recent discovery, they look set to have a very exciting future in
the macrocyclic world.
Acknowledgements
We wish to acknowledge the use of the EPSRC’s Chemical
Database Service at Daresbury. KS thanks the University of
Brighton for a Research Studentship.
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