Pseudo[1]Catenane-Type Pillar[5]thiacrown Whose Planar Chiral Inversion is Triggered by Metal Cation and Controlled by Anion

Article abstract of DOI:10.1021/jacs.8b05751

Chiral inversion of single molecules has been a challenging task because chirality information controls structures and functions of various molecules, artificial nanostructures, DNA, and proteins. Herein we present a pseudo[1]catenane-type molecule whose

Full text of DOI:10.1021/jacs.8b05751

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Article
pseudo[1]Catenane-Type Pillar[5]thiacrown Whose Planar Chiral
Inversion is Triggered by Metal Cation and Controlled by Anion
Eunji Lee, Huiyeong Ju, In-Hyeok Park, Jong Hwa Jung, Mari
Ikeda, Shunsuke Kuwahara, Yoichi Habata, and Shim Sung Lee
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b05751 • Publication Date (Web): 05 Jul 2018
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pseudo[1]Catenane-Type Pillar[5]thiacrown Whose Planar Chiral In-
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version is Triggered by Metal Cation and Controlled by Anion
Eunji Lee,† Huiyeong Ju,† InꢀHyeok Park,† Jong Hwa Jung,† Mari Ikeda,‡ Shunsuke Kuwahara,§ Yoichi
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Habata,*,§ and Shim Sung Lee*,†
†Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, S. Korea
‡Department of Chemistry, Education Center, Faculty of Engineering, Chiba Institute of Technology, 2ꢀ1ꢀ1 Shibazono, Naꢀ
rashino, Chiba 275ꢀ0023, Japan
§Department of Chemistry, Faculty of Science, Toho University, 2ꢀ2ꢀ1 Miyama, Funabashi, Chiba 274ꢀ8510, Japan
ABSTRACT: Chiral inversion of single molecules has been a challenging task because chirality information controls structures
and functions of various molecules, artificial nanostructures, DNA, and proteins. Herein we present a pseudo[1]catenaneꢀtype molꢀ
ecule whose planar chiral inversion is driven by a metal ion under the control of anions for the first time. Considering an in-out
equilibrium of a fused thiacrown and the soft metal binding, pillar[5]thiacrown (racꢀL) was synthesized. Two planarꢀchiral enanꢀ
tiomers of racꢀL (in-pSꢀL and in-pRꢀL) were isolated and the absolute configuration was determined by circular dichroism and
single crystal Xꢀray analysis. The in-pSꢀL recognizes Hg2+ to trigger the chiral inversion to out-pR-L, to our surprise; it takes
−
−
place only in the presence of ClO4 or NO3 among the anions used. In the mercury(II) perchlorate complex solution, anionꢀ
−
exchange from ClO4 to I− or removal of Hg2+ by addition of S2− makes the system reversible. The crystallographic approach reꢀ
veals that the anions act as coordination modeꢀdirecting species (endo- or exo-coordination) which play a decisive role on the
−
chiral inversion. For instance, the week coordinating ClO4 allows Hg2+ to locate inside the thiacrown (endoꢀcoordination) which
causes the chiral inversion from in-pSꢀL to out-pRꢀL due to the expansion of the thiacrown unit upon endoꢀmode complexation.
Oppositely, the strong coordinating I− takes Hg2+ out of the thiacrown (exoꢀcoordination) without large conformational changes of
the thiacrown, resulting in no chiral inversion. A series of experimental works was also accomplished with the other enantiomer in-
pRꢀL, which afforded identical results. Consequently, the chiral inversion is governed by steric factors that arise from the coordinaꢀ
tion modes depending on the coordinating ability of anions. This work demonstrates the first chiral inversion induced by combinaꢀ
tion of metal ion and anion, and presents a new perspective on the supramolecular coordination chemistry of pillar[n]arenes.
As early as 1998, Stoddart group reported an achiral pseu-
do[1]catenaneꢀtype chromophoric switching system recognizꢀ
ing tetrathiafulvalene (TTF) via an inꢀout equilibrium of a
fused crown ring.44 Following the pioneering work on pilꢀ
lar[5]arenes by Ogoshi in 2008,45 a large number of derivaꢀ
tives has been introduced for selfꢀassemblies with a range of
organic guests to fabricate mechanically interlocked supraꢀ
molecules.46ꢀ50 Due to the substitution position of alkoxy
groups, pillararenes have the planar chirality and the hinꢀ
dered rotation of aromatic units allows to have two stable
enantiomers (pS and pR).51,52 For the isolation of the enanꢀ
tiomers from racemic mixture, the modification with bulky
substituents is beneficial due to the hindered rotation.53 In
this sense, pillar[5]arenes modified with pendant arms or a
fused ring have been employed to perform the planar chiral
inversions by external stimuli such as temperature,54 solꢀ
vent,55 and organic guest56 as illustrated in Figure 1.
INTRODUCTION
Chiral inversion has attracted much attention not only because
of the relation with fascinating physicochemical phenomena
and biofunctions observed in biology1ꢀ4 but also for underꢀ
standing of the assembly mechanisms of helical nanostructures
in materials science and nanobiotechnology5ꢀ8. Hence the conꢀ
trolled chiral inversion of artificial systems which involve
polymerꢀbased assemblies and supramolecular aggregates
have been reproduced upon exposure to external stimuli such
as temperature,9ꢀ11 light,12ꢀ16 solvent,17ꢀ20 pH,21 metal ion,22ꢀ26
anion,27ꢀ29 redox30,31, and achiral guest32,33. Usually many cases
of chiral nanostructures originate from their molecular chiraliꢀ
ty. Thus, to understand the mechanistic process of both chiral
inversion of single molecules and helical inversion of
nanostructures, it is of critical importance to clarify the main
driving forces at a molecular level. However most of the reꢀ
ported chiral inversions have focused on selfꢀassembled oligoꢀ
or polymeric species, examples of single molecules especially
mediated by metal ion are very rare.34,35 In particular, planar
chiral molecules have been applicable in molecular recogniꢀ
tion,36,37 catalysts,38,39 and molecular motors.40ꢀ43 Therefore, it
is challenging to develop a smart molecular system whose
planar chiral inversion is triggered by metal ion complexation
or combination of metal ion and anion.
Figure 1. Stimuliꢀtriggered planar chiral inversion of pilꢀ
lar[5]arene derivatives.
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In spite of the huge progress on pillar[n]arenes in a
trollable64,65 and this result make them more attractive because
of applications in onꢀoff type photophysical chemosensors as
well as for understanding the sensing mechanism.66ꢀ68
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short period, their supramolecular coordination compounds
have still been an unexplored research area due to too large
cavities and lack of metal binding sites.57 Thus, the sophistiꢀ
cated modification of a pillar[n]arene scaffold for metal bindꢀ
ing, remains a challenge. In this study, we wished to explore
the metal ionꢀdriven chiral inversion of pillar[5]arene via the
rational modification of its parent structure because metal ions
are an essential factor in particular biosystems. For this, we
have proposed a bicyclic pillar[5]ꢀthiacrown (racꢀL, Scheme
1a) incorporating a fused ‘thiacrown’ because of its propensity
for recognizing soft metal ions.58ꢀ60 As shown in Scheme 1c,
each of two expected enantiomers (pSꢀL and pRꢀL) of racꢀL
has an in-out equilibrium, thus racꢀL is expected to have four
conformers such as in-pSꢀL, in-pRꢀL, out-pSꢀL, and out-pRꢀL.
Based on the design concept and preliminary results, the
advantage of using racꢀL is that it might be a candidate which
realizes the metalꢀdriven chiral inversion because of the folꢀ
lowing reasons. (i) The two enantiomers (pSꢀL or pRꢀL) are
expected to be resolvable due to the large fused thiacrown. (ii)
Upon soft metal binding to thiacrown, the expected coordinaꢀ
tion modes may play a role in inversion events. (iii) Monitorꢀ
ing of these phenomena might be helpful for the mechanistic
understanding. In the process of the listed aspects (iꢀiii) have
been subsequently tested, we found a new type of metalꢀdriven
chiral inversion system. Herein we report a first example of
single molecule whose chiral inversion is triggered by metal
ion complexation under the control of anions which act as
coordination modeꢀdirecting species.
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Scheme 1. (a) rac-L (Only pS-L is Shown), (b) Reference
Thiacrown L’, (c) The “in-out” Equilibria, and (d) Endo-
and Exo-coordination Modes of Thiacrown
RESULTS AND DISCUSSION
Soft metal binding site
Synthesis of Pillar[5]thiacrown (rac-L). The target bicyclic
pillar[5]ꢀthiacrown (rac-L) was synthesized by a coupling
reaction between dibromo pillar[5]arene69 and the dithiol in
the presence of K2CO3 in acetonitrile (yield 40 %, Figure 2a).
According to NMR spectra of rac-L and reference thiacrown
L’70 (Scheme 1b) in CDCl3, it is found that rac-L favors a
pseudo[1]catenane configuration (inꢀL) in which the fused
thiacrown ring is included inside the pillar[5]arene cavity
(Figures S1ꢀS3). For example, thiacrown ring signals, espeꢀ
cially HcꢀHe appear significantly upfield (0.95ꢀ2.20 ppm)
compared with those of L’ (2.70ꢀ3.30 ppm) due to the
strong shielding effect. The racemic mixture rac-L showed
no circular dichroism (CD) signals (Figure S4).
Single crystals of racꢀL were grown by slow evaporation
from its CHCl3 solution. In crystal, racꢀL has a pseu-
do[1]catenane configuration (in-racꢀL) which exists as a raꢀ
cemic mixture (inꢀpR-L and inꢀpS-L) (Figure S5). Notably, the
fused thiacrown is elongated to fit pillar[5]arene interior stabiꢀ
lizing pseudo[1]catenane via CH···π interactions with distancꢀ
es of 2.56ꢀ2.99 Å (Figure S6). The two sulfur atoms in the
thiacrown ring are oriented toward the outside of the cavity.
HPLC Resolution and Assignment of the Enantiomers.
A modification with a properꢀsized thiacrown enabled the
resolution of rac-L into a couple of enantiopure pRꢀL and pSꢀ
L. Upon injection of rac-L onto a preparative chiral HPLC
column, two peaks of equal area were observed and these two
fractions (F1 and F2) were collected (Figure 2b and Figure
S7a). Reꢀinjection of F1 or F2 exhibited a single peak at the
same position of each fraction, indicating that no racemization
between F1 and F2 occurs (Figure S7b,c). The CD spectrum of
F1 exhibits a negative Cotton effect at λext = 309 nm, while
that of F2 shows a positive one at the same wavelength (Figꢀ
ure 2c). Fortunately, it was possible to obtain single crystals
both from F1 and F2 (Figure 2d). Based on the crystal strucꢀ
tures, F1 and F2 were assigned to in-pSꢀL and in-pRꢀL, reꢀ
spectively.
S
S
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
S
S
Soft metal binding site
rac-L
L'
(pS-L + pR-L)
(Reference thiacrown)
(b)
(a)
Enatiomeric Pair
H3CO
O
S
O
OCH3
S
CH2
O
CH2
H3CO
O
OCH3
O
O
4
4
O
O
S
S
in-pR-L
in-pS-L
"in-out" Equilbrium via
Planar Chiral Inversion
O
O
S
S
H3CO
CH2
OCH3
CH2
O
O
OCH3
H3CO
4
O
4
O
O
O
S
S
out-pR-L
out-pS-L
(c)
(d)
R
R
M
X
S
S
S
S
X
M
M
Endo-coordination
Exo-coordination
The fused thiacrown has potent metal (M) binding sites
via SꢀM bonds which might induce the metal binding inside
(endoꢀcoordination) or outside (exoꢀcoordination) the thiaꢀ
crown (Scheme 1d).61ꢀ63 We previously reported a series of
thiacrowns that form diverse types of soft metal complexes
depending on the coordination modes.60ꢀ63 In our experience,
the endoꢀ and exoꢀcoordination modes are conditionally conꢀ
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Figure 2. (a) Synthetic scheme of racꢀL, (b) resolution of the enantiomers [fraction 1 (F1) and fraction 2 (F2)] of racꢀL by a preparative
chiral HPLC, (c) the CD spectra of F1 and F2, and (d) crystal structures of (left) Fl assigned to in-pSꢀL and (right) F2 assigned to in-pRꢀL.
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CD Study for the Metal Ion Induced Chiral Inversion.
In order to investigate the recognition ability of metal ions
(Na+, Ag+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, and Hg2+)
and the related behaviors including the chiral inversion, in-pSꢀ
L was employed in the CD measurement (Figure 3). Considerꢀ
ing the solvent effect on the chiral inversion CHCl3/CH3OH
(1:2.5) was employed (Figure S10). Metal perchlorates were
used due to the influence of anions, which are described in the
latter part. Interestingly, when Hg2+ was added to in-pSꢀL, a
negative Cotton effect at 309 nm in the CD spectrum was inꢀ
verted in sign to give a positive one, indicating that the inverꢀ
sion of planar chirality happened from in-pSꢀL to out-pRꢀL
(Figure 3). Some thiaoxaꢀmacrocycles have been known to
form stable complexes with Hg2+ via the strong HgꢀS bonding
due to the thiaphilic nature.66 In sharp contrast, other metal
ions show no significant spectral changes except Ag+ which
shows the disappearance of the almost of negative peak due to
Figure 3. CD spectral change of in-pSꢀL (0.04 mM, blue color) in
the presence of metal perchlorates (5.0 equivalents) in
CHCl3:CH3OH (v/v 1:2.5). (Inset) Proposed representation of the
Hg2+ꢀtriggered chiral inversion.
the partial chiral inversion (Figure S11). Consequently, the CD
results indicate that Hg2+ induces the chiral inversion quite
selectively probably due to a favorable complexation of thiaꢀ
crown.66 In case of Ag+, it could be possible to explain the
result similarly but the observed metal ion effect is less (Figꢀ
ure S11).
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−
CD Titration with Mercury(II) Perchlorate. In an atꢀ
tempt to probe the origin of the above Hg2+ꢀtriggered chiral
inversion, the influence of the mercury(II) complexation on
the chiral inversion was investigated by CD titration (Figure
4). When mercury(II) perchlorate (0.0ꢀ5.0 equivalents) was
added to in-pSꢀL, the intense negative CD Cotton effect at 309
nm was gradually decreased and was inverted to positive ones
above 2 equivalents. Then the positive signal increases graduꢀ
ally until around 3 equivalents and then no significant spectral
changes are observed, indicating that the chiral inversion from
inꢀpS to outꢀpR upon Hg2+ complexation.
Under similar conditions, UVꢀvis titration was carried out
by addition Hg(ClO4)2 into in-pSꢀL solution (Figures S13 and
S14). According to the spectral changes, the association conꢀ
stant (log K) for a 1:1 (metalꢀtoꢀligand) complexation was
calculated to be 4.1(1) by a nonlinear curve fitting method.71
However, the corresponding titration with HgI2 showed a less
stable and nonꢀstoichiometric behavior probably due to the
inhibition of the strong coordinating nature of I− (Figure S15).
Cl−, Br−, I−, CF3CO2 , and SCN− show no CD spectral changes
(Figure 5). The unexpected finding indicates that this is the
unique metal ionꢀtriggered and anionꢀcontrolled chiral inverꢀ
sion system, which has not been reported so far. The related
mechanistic studies are discussed in the later parts.
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CD Study on the Reversible Inversion of Chirality. In
order to clarify the reversibility of the anionꢀcontrolled chiral
inversion, an anionꢀexchange based twoꢀstage titration was
carried out. In the first stage, Hg(ClO4)2 (0ꢀ5.0 equivalents)
was added stepwise to in-pSꢀL (dashed lines in Figure 6), then
Iꢀ (0ꢀ5.0 equivalents, as Bu4NI; solid lines in Figure 6) was
titrated consecutively. During the second stage titration with
I−, the increased positive signal by Hg(ClO4)2 (in the first
stage) decreases gradually, and its signal was changed to the
negative and eventually the intensity is almost recovered (blue
lines in Figure 6). The results suggest that by performing the
reverse direction via the anionꢀexchange, the reversible chiral
inversion from inꢀpSꢀL via outꢀpRꢀL to inꢀpSꢀL was conꢀ
firmed (red arrows in Scheme 2). Meanwhile, the titration with
Bu4NClO4 to a mixture of inꢀpSꢀL and HgI2 (5.0 equivalents)
shows no CD spectral changes (Figure S17), reflecting that no
anionꢀexchange occurs because of the weaker coordination
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ability of ClO4 than that of I− (green arrows in Scheme 2).
−
The anionꢀexchange for the corresponding system was also
confirmed by a series of the ESIꢀMS experiments (Figure
S18).
Figure 4. CD spectral changes of inꢀpSꢀL (0.04 mM) upon addiꢀ
tion of Hg(ClO4)2 (0.0ꢀ5.0 equivalents) in CHCl3:CH3OH (1:2.5).
Role of Anions in the Mercury(II)-Triggered Chiral
Inversion. While investigating the metal ion driven chiral
inversion observed above, spectral dependences on the anions
employed were also observed. To our surprise, the Hg2+ꢀ
triggered chiral inversion in the CD probe was effectively
Figure 6. CD spectral changes of a mixture of inꢀpSꢀL (0.04 mM)
and Hg(ClO4)2 (5.0 equivalents) upon addition of Bu4NI (0.0−5.0
equivalents) in CHCl3/CH3OH (1:2.5).
−
observed only in the presence of ClO4− or NO3 anion system;
the addition of mercury(II) salts with the other anions such as
Scheme 2. Chiral Inversion by Complexation with
Hg(ClO4)2 and Reverse Chiral Inversion by Anion-
Exchange
Having confirmed the reversibility via the anionꢀexchange,
one more direct confirmation of the reversibility is to remove
Hg2+ from the mercury(II) perchlorate complex formed in the
first stage titration in Figure 6. When excess amount of S2− (as
Na2S) was added to the mixture of in-pS-L and Hg(ClO4)2 (5.0
Figure 5. Hg2+ꢀtriggered CD spectral changes of in-pSꢀL which
shows the anionꢀcontrolled chirality inversion in CHCl3/CH3OH
(1:2.5).
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equivalents), the positive CD signal was changed to the negaꢀ
ure 8e,f, blueꢀmarking area). This result indicates that addition
of Hg(ClO4)2 followed by anionꢀexchange with I− performs the
reversible chiral inversion.
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tive and its intensity was almost recovered by decomplexation
(Figure 7 and Scheme 3). In this case, the complex solution
changed from colorless to dark gray implying the formation of
HgS precipitate (see the photo in Figure 7c).
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Figure 7. CD spectra of (a) inꢀpSꢀL (0.04 mM), (b) inꢀpSꢀL +
Hg(ClO4)2 (5.0 equivalents), and (c) inꢀpSꢀL + Hg(ClO4)2 (5.0
equivalents) + Na2S (excess) in CHCl3:CH3OH (1:2.5). Photo:
When Na2S was added to the Hg(ClO4)2 complex solution, a dark
gray precipitate (HgS) was formed.
1
Figure 8. H NMR (500 MHz) spectra of inꢀpSꢀL (aꢀd) in the
presence of Hg(ClO4)2 (0ꢀ3 equivalents) and (e and f) after sucꢀ
cessive addition of NaI (5 and 10 equivalents) [inꢀpSꢀL] = 0.5
mM in CDCl3/CD3OD (1:2.5). The peaks marked with circles and
reciprocal triangles indicate solvents (hexane and water) and
spinning sideband, respectively. The cartoon in the right side
shows the conformational changes of the ligand part in each comꢀ
plex.
Scheme 3. Reversible Chiral Inversion by Complexation
and Decomplexation
Hg(ClO4)2
Complexation
Decomplexation
Crystallographic Approach toward the Anion Effect
on the Chiral Inversion. Since the anion effect on the Hg2+ꢀ
triggered chiral inversion is assumed to be associated with the
structures of the corresponding species, we wanted to prepare
related complexes to access the influence of anions on the
chiral inversion. Fortunately, we isolated a perchlorate comꢀ
plex 1 and an iodide complex 2 suitable for the Xꢀray analysis
L
out-pR- /Hg(ClO4)2
in-pS-L
S2-
HgS
NMR Study on the Chiral Inversion. Comparative
NMR studies were performed for further understanding of the
metal ionꢀtriggered and anionꢀcontrolled chiral inversion. As
−
1
in addition to inꢀpSꢀL (Figure 9). As mentioned, ClO4 allows
mentioned above, H NMR spectrum (Figure 8a) shows that
the chiral inversion, while I− shows no chiral inversion.
pSꢀL favors a pseudo[1]catenane conformation (inꢀpSꢀL) same
as observed in the CD study and crystal structure. When 0.5 or
1.0 equivalent of Hg(ClO4)2 was added, peaks for in-pSꢀL are
broadened with small downfield shifts and the areas gradually
decreased due to coexisting of in-pSꢀL and Hg2+ꢀ(out-pRꢀL)
species whose dynamic behaviors are slow on the NMR time
scale (Figure 8b,c). Notably, further addition of Hg(ClO4)2
above 3.0 equivalents led to the complete disappearance of the
peaks for Hc, Hd, and He in the upfield area (0.9−2.2 ppm,
Figure 8d). Instead, those of the corresponding peaks appear
at a lower field (3.5−3.9 ppm, redꢀmarking area) with a series
of badly resolved peaks, indicating that the chiral inversion
occurs from in-pS-L to out-pR-L. As a second stage, when
excess amount of iodide (as NaI) was added to the mixture of
in-pSꢀL and mercury(II) perchlorate, peaks for in-pS-L graduꢀ
ally appeared and eventually recovered at 10 equivalents (Figꢀ
In the crystal structure of the perchlorato complex 1,
[Hg(out-pRꢀL)(ClO4)2] (Figure 9b), the bicyclic ligand shows
outꢀpRꢀL conformation in which the mercury(II) atom (Hg1)
locates at the center of thiacrown adopting an endoꢀ
coordination mode. The Hg1 atom is hexaꢀcoordinate, being
bound to O2S2 donors in thiacrown and the coordination
sphere is completed by two monodentate perchlorate O atoms
via weak HgꢀO bonds (Hg1ꢀO13 2.683(8) and Hg1ꢀO17
2.660(7) Å). Meanwhile, iodo complex 2, [(Hg2I4)2(inꢀpSꢀL)3],
is an oligomeric species in which the bicyclic ligand maintains
in-pS-L conformation (Figure 9c). Indeed, the arrangement of
three ligands (two terminal and one central), metal ions, and
anions in 2 is unique, with an exoꢀcoordination mode. For
example, two mercury(II) atoms (Hg1 and Hg2) locate out of
thiacrown, forming a squareꢀtype Hg2I4 cluster and these two
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−
clusters link three in-pS-L ligands to generate a club sandwich coordination is due to weaker coordination ability of ClO4
type 2:3 (clusterꢀtoꢀligand) complex72,73 via HgꢀS bonds [Hg1ꢀ
S2 2.632(4) and Hg1ꢀS3 2.526(4) Å]. In the ESIꢀMS measꢀ
urement for 2, however, the 1:1 complex [(inꢀpSꢀL)·HgI]+ was
confirmed as a major species (Figure S19). We previously
proposed silver(I) complexes of an S2O3ꢀmacrocycle exhibitꢀ
ing endoꢀ or exoꢀcoordination modes due to the different coorꢀ
dinating ability of anions.64 Several mercury(II) complexes of
NO2S2ꢀmacrocycles which generalize this coordination behavꢀ
ior have been applied to explain anionꢀcontrolled color66,67 and
fluorescence68 chemosensors.
which draws Hg2+ into thiacrown cavity (‘Pull’ the Hg2+ into
the thiacrown cavity). In this case, the thiacrown is largely
expanded and rigidified because the S1ꢀO2ꢀO3ꢀS2 segment is
rearranged via the HgꢀS and HgꢀO bond formations, leading to
a GGG arrangement between two adjacent donors. Thus, the
endoꢀcoordinated thiacrown (0.70 × 0.71 nm) is too large to
remain inside the pillar[5]arene and eventually inverted to the
out-pS-R conformer to minimize the repulsive force. In the
iodo complex 2, the conformation of thiacrown is quite similar
to that of free in-pSꢀL. For example, the S1ꢀO2ꢀO3ꢀS2 segꢀ
ment in 2 has a TTG arrangement and two Hg2+ atoms are
bound to sulfur donors from out of thiacrown, maintaining the
ellipsoidal shape with the size of 0.45 × 0.94 nm. Consequentꢀ
ly, as shown in Figure 10 and Table 1, the chiral inversion is
controlled by steric factors that arise from the coordination
modes depending on the coordinating ability of anions.
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Table 1. The relevant conformational parameters of thia-
crown unit in in-pS-L, 1, and 2
Interdonor
(a)
(b)
Coordination
mode
Overall
conformation
Dimension
(nm)
Crystal
arrangement
(S1ꢀO2ꢀO3ꢀS2)
in-pSꢀL
TTG
GGG
TTG
ellipsoid (in) 0.41×0.98
near circle (out) 0.70×0.71
ellipsoid (in) 0.45×0.94
−
1 (ClO4 )
2 (I−)
endo
exo
(c)
In the CD studies, the difference of the CD intensities was
observed during the chiral inversion (Figures 3ꢀ7). Basically,
the CD intensity is sensitive to the conformational change of
chromophores and the distribution of enantiomers. In the
NMR study, however, in-pS-L is completely converted to 1
(Figure 8). So the incomplete inversion of some aromatic units
in the pillar[5]arene unit may lead the difference of the CD
intensities as observed in the crystal structures (Figure S20).
Indeed, almost the same series of experimental works was
also accomplished with the other enantiomer in-pRꢀL (Figures
S21ꢀS28) and the results are identical to those of in-pSꢀL alꢀ
ready mentioned above. As summarized in Figure 11, the moꢀ
lecular level information obtained from the Xꢀray crystallogꢀ
raphy, CD, and NMR experiments provide a clearer picture
that the anion plays a decisive coordination modeꢀdirecting
role, as it has been also observed in the formations of endoꢀ or
exoꢀcoordination of simple thiamacrocycles by us previousꢀ
ly.64,65 Indeed, the weakly coordinated perchlorato ligands
allow the endoꢀcoordination by pushing the Hg2+ into the thiaꢀ
crown cavity and thus resulting in the chiral inversion. While,
Figure 9. Crystal structures of (a) inꢀpSꢀL, (b) mercury(II) perꢀ
chlorate complex [Hg(outꢀpRꢀL)(ClO4)2] (1) with an endoꢀ
coordination mode, and (c) mercury(II) iodide complex
[(Hg2I4)2(inꢀpSꢀL)3] (2) with an exoꢀcoordination mode.
Mechanistic Study of the Chiral Inversion. Crystal
structures of the Hg2+ complexes clearly illustrate that the en-
doꢀ or exoꢀcoordination mode is anionꢀdependent and only the
endoꢀcoordination is a driving force for the chiral inversion.
For the mechanistic understanding more systemically, the deꢀ
tailed crystal structures of the corresponding species are comꢀ
pared (Figure 10) and summarized in Table 1. In the free in-
pSꢀL, the semiꢀflexible thiacrown shows an ellipsoidal shape
(0.41 × 0.98 nm) which stabilizes the pseudo[1]catenane form
via CH···π interactions (Figure S9). As can be seen in Figure
9a, the S1ꢀO2ꢀO3ꢀS2 segment in the thiacrown shows a TTG
arrangement (T: trans, G: gauche) between two adjacent doꢀ
nors, adopting a rodꢀlike shape threading the pillar[5]arene.
In the perchlorato complex 1, the preferred endoꢀ
Figure 10. Structural comparison of thiacrown units (spaceꢀfilling presentation) in in-pSꢀL, 1, and 2 (terminal part), showing the anions
as coordination modeꢀdirecting species.
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Figure 11. Cartoon representation for the mechanistic illustration of the cationꢀselective and anionꢀcontrolled planar chiral inversion.
Preparation of L. To a refluxed solution of K2CO3 (0.44 g,
the strongly coordinated iodo ligands pushes the Hg2+ out of
the thiacrown cavity stabilizing the pseudo[5]catenane and no
chiral inversion occurs. Consequently, the “Push-and-Pull”
process serves to explain how the anions with different coorꢀ
dinating ability to control the observed chiral inversion
through the formations of the endoꢀ or exoꢀcoordinated comꢀ
plexes.
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3.18 mmol) and 4 (1.00 g, 1.07 mmol) in acetonitrile (100 mL)
was added dropwise a solution of 3,6ꢀdioxaꢀ1,8ꢀoctanedithiol
(0.23 g, 1.26 mmol) in acetonitrile (100 mL) under nitrogen, and
the reaction mixture was refluxed for a further 48 h. After cooling
to room temperature, the solvent was evaporated and the residue
was extracted with dichloromethane. The combined organic phasꢀ
es were dried with anhydrous sodium sulfate and then evaporated
to dryness. The flash column chromatography (SiO2; 20 % ethyl
acetate: nꢀhexane) afforded the product as a white solid in 40%
CONCLUSION
1
yield. Mp: 216ꢀ218 °C. H NMR (500 MHz, CDCl3): δ 6.93ꢀ6.83
In summary, we for the first time have prepared a pseu-
do[1]catenaneꢀtype single molecule in-pS-L that shows planar
chirality inversion upon metal complexation stimulus under
the control of anions. The molecular level information obꢀ
tained from Xꢀray crystal structures of the mercury(II) comꢀ
plexes and results from the systematic CD and NMR titrations
provide a clearer picture how the endoꢀcoordination of Hg2+
triggers the chiral inversion in combination to the specific
(weak coordinating) anions. This result adds to a family where
the chiral inversion of single molecules occurs by externalꢀ
stimuli. In relation to the unique combination of cation and
anion in the chiral inversion, the mechanistic illustration proꢀ
posed here could be instructive for a deeper understanding and
design of chiral materials and devices where metal ions and
anions are in close proximity. Also this result can motivate the
metallosupramolecular studies of pillar[5]arene derivatives
which remain an unexplored area so far.
(m, 10H, Ar), 4.31ꢀ4.08 (m, 4 H, ArOCH2CH2S), 3.86ꢀ3.72 (m, 34
H, ArCH2Ar and OCH3), 2.82ꢀ2.41 (m, 4 H, ArOCH2CH2S), 2.10ꢀ
1.99 (m, 4 H, OCH2CH2O), 1.84 (m, 4 H, SCH2CH2O), 1.38ꢀ0.92
(m, 4 H, SCH2CH2O). 13C NMR (125 MHz, CDCl3): 150.46,
150.45, 150.44, 150.23, 148.55, 128.40, 128.30, 127.85, 127.73,
127.56, 115.12, 114.80, 113.47, 113.34, 113.30, 69.99, 68.81,
68.14, 55.68, 55.58, 55.49, 55.14, 30.11, 29.50, 29.39, 29.31,
28.40. IR (KBr pellet): 2983, 2933, 2909, 2948, 2852, 2827, 1502,
1466, 1400, 1373, 1307, 1213, 1127, 1108, 1048, 1003, 930, 877,
853, 771, 701, 670, 649 cmꢀ1. Anal. calcd. for [C53H64O12S2]: C,
66.50; H, 6.74; S, 6.70. Found: C, 66.61; H, 6.52; S, 6.43%. Mass
spectrum: m/z = 979.83 [C53H64O12S2Na]+.
Resolution of enantiomer with chiral-probe HPLC. YMC
CHIRAL ART CelluloseꢀSB; Mobile phase: ethanol:nꢀhexane
(1:9) with elution speed 4.0 mL/min; Detection wavelength: 300
nm; Temperature: room temperature.
Preparation of [Hg(out-pR-L)(ClO4)2] (1). In a glass tube
(i.d. 5 mm), Hg(ClO4)2·xH2O (25.1 mg, 0.063 mmol) in methanol
(2 mL) was slowly diffused onto a solution of inꢀpSꢀL (20.0 mg,
0.021 mmol) in chloroform (2 mL). After 2 days, the colorless Xꢀ
ray quality single crystals 1 were obtained. Yield (45%). IR (KBr
pellet): 2930, 2828, 1501, 1466, 1401, 1303, 1213, 1095, 1043,
926, 880, 671, 650, 623 cmꢀ1. Anal. calcd. for
[C53H64HgCl2O20S2]: C, 46.92; H, 4.75; S, 4.73. Found: C, 46.81;
H, 4.61; S, 4.66%.
EXPERIMENTAL SECTION
General. All chemicals and solvents used in the syntheses
were of reagent grade and were used without further purification.
NMR spectra were recorded on a Bruker 500 spectrometer (500
MHz). The CD spectra were recorded on a JASCO Jꢀ815 CD
spectrophotometer. CD spectra were determined over the range of
240ꢀ350 nm using a quartz cell with 1.0 mm path length. Scans
were taken at a rate of 100 nm/min with a sampling interval of 1.0
nm and response time of 1 s. The absorption spectra were recordꢀ
ed on a Scinco Sꢀ3150 UVꢀvisible spectrophotometer. The FTꢀIR
spectra were measured with a Nicolet iS10 spectrometer. The
ESIꢀmass spectra were obtained on a Thermo Scientific LCQ
Fleet spectrometer. Each product obtained in this work was dried
in a vacuum before elemental analysis, which was carried out on a
Thermo Scientific Flash 2000 Series elemental analyzer.
[(Hg2I4)2(in-pS-L)3] (2). HgI2 (28.5 mg, 0.063 mmol) in
methanol (2 mL) was added to a solution of inꢀpSꢀL (20.0 mg,
0.021 mmol) in chloroform (2 mL). Slow evaporation of the soluꢀ
tion afforded a pale yellow crystalline product 2 suitable for Xꢀray
analysis. Yield (60%). Mp: 195ꢀ197 °C. IR (KBr pellet): 2934,
2852, 2826, 1499, 1465, 1399, 1308, 1214, 1099, 1047, 928, 879,
854, 773, 702, 670, 648 cmꢀ1. Anal. calcd. for
[C159H192Hg4I8O36S6]: C, 40.73; H, 4.13; S, 4.10. Found: C, 40.75;
H, 4.15; S, 4.16%.
CAUTION! Mercury and cadmium complexes are toxic. Perꢀ
chlorate salts of metal complexes are potentially explosive and
should be handled with great care.
ASSOCIATED CONTENT
Supporting Information. NMR spectra, Crystal structures, CD
spectra, UVꢀvis spectra, and Xꢀray crystallographic files (CIF
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(19) Nagata, Y.; Yamada, T.; Adachi, T.; Akai, Y.; Yamamoto, T.;
format) are included. This material is available free of charge via
the Internet at http://pubs.acs.org.
Suginome, M. J. Am. Chem. Soc. 2013, 135, 10104ꢀ10113.
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Accession Codes
CCDC 1844158 (racꢀL), 1844159 (inꢀpSꢀL), 1844160 (inꢀpRꢀL),
1844161 (1), and 1844162 (2) contain the supplementary crystalꢀ
lographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Authors
(27) Suk, J.ꢀm.; Naidu, V. R.; Liu, X.; Lah, M. S.; Jeong, K.ꢀS. J.
Am. Chem. Soc. 2011, 133, 13938ꢀ13941.
(28) Miyake, H.; Kamon, H.; Miyahara, I.; Sugimoto, H.; Tsukube,
H. J. Am. Chem. Soc. 2008, 130, 792ꢀ793.
*Eꢀmail: habata@chem.sci.tohoꢀu.ac.jp
*Eꢀmail: sslee@gnu.ac.kr
(29) Miyake, H.; Yoshida, K.; Sugimoto, H.; Tsukube, H. J. Am.
Chem. Soc. 2004, 126, 6524ꢀ6525.
(30) Ohta, E.; Sato, H.; Ando, S.; Kosaka, A.; Fukushima, T.;
Hashizume, D.; Yamasaki, M.; Hasegawa, K.; Muraoka, A.;
Ushiyama, H.; Yamashita, K.; Aida, T. Nat. Chem. 2011, 3, 68ꢀ
73.
(31) Gregoliński, J.; Hikita, M.; Sakamoto, T.; Sugimoto, H.; Tsuꢀ
kube, H.; Miyake, H. Inorg. Chem. 2016, 55, 633ꢀ643.
(32) Liu, G.ꢀF.; Zhu, L.ꢀY.; Ji, W.; Feng, C.ꢀL.; Wei, Z.ꢀX. Angew.
Chem., Int. Ed. 2016, 55, 2411ꢀ2415.
(33) Deng, M.; Zhang, L.; Jiang, Y.; Liu, M. Angew. Chem., Int. Ed.
2016, 55, 15062ꢀ15066.
(34) Haberhauer, G. Angew. Chem., Int. Ed. 2010, 49, 9286ꢀ9289.
(35) Kokan, Z.; Perić, B.; Vazdar, M.; Marinić, Z.; VikićꢀTopić, D.;
Meštrović, E.; Kirin, S. I. Chem. Commun. 2017, 53, 1945ꢀ
1948.
(36) Yamamura, M.; Saito, T.; Nabeshima, T. J. Am. Chem. Soc.
2014, 136, 14299ꢀ14306.
(37) Ogoshi, T.; Saito, K.; Sueto, R.; Kojima, R.; Hamada, Y.;
Akine, S.; Moeljadi, A. M. P.; Hirao, H.; Kakuta, T.; Yamagꢀ
ishi, T.ꢀa. Angew. Chem., Int. Ed. 2018, 57, 1592ꢀ1595.
(38) Hu, B.; Meng, M.; Wang, Z.; Du, W. T.; Fossey, J. S.; Hu, X.
Q.; Deng, W. P. J. Am. Chem. Soc. 2010, 132, 17041ꢀ17044.
(39) Maeda, R.; Wada, T.; Mori, T.; Kono, S.; Kanomata, N.; Inoue,
Y. J. Am. Chem. Soc. 2011, 133, 10379ꢀ10381.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by NRF (2016R1A2A2A05918799 and
2017R1A4A1014595), South Korea. The Support Program for
Strategic Research Foundation at Private Universities (S1201034)
and KAKENHIꢀPROJECTꢀ17K05844 from the Ministry of Eduꢀ
cation, Sports, Science and Technology of Japan are acknowlꢀ
edged.
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SYNOPSIS TOC
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A pseudo[1]catenaneꢀtype pillar[5]thiacrown (inꢀpSꢀL) whose planar chiral inversion is driven by a metal ion under the
control of anions is reported. In the mercury(II) perchlorate complex (1) solution, anionꢀexchange or removal of Hg2+ makes
the system reversible.
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