Acid/base- and base/acid-switchable complexation between anionic-/cationic-pillar[6]arenes and a viologen ditosylate salt

Article abstract of DOI:10.1039/c9ob00398c

Two new host-guest complexes between water-soluble anionic pillar[6]arene (WP6) or cationic pillar[6]arene (CP6) and a viologen ditosylate salt G·2TsO were constructed, among which one formed from WP6 and G²⁺ ions can be controlled by the sequential addition of an acid and a base (HCl and NaOH, respectively), whereas the other fabricated from CP6 and TsO^- ions can be switched through the sequential addition of basic and acidic reagents (NaOH and HCl, respectively).

Full text of DOI:10.1039/c9ob00398c

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Acid/base‐ and base/acid‐switchable complexationes between
anionic‐/cationic‐pillar[6]arenes and a viologen ditosylate salt
Qunpeng Duan,*a Hongsong Zhang a, Wenpeng Maia, Fei Wang*a and Kui Lu*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Two new host‐guest complexations between water‐soluble neutral14 water‐soluble pillararenes have been synthesized and
anionic pillar[6]arene (WP6) or cationic pillar[6]arene (CP6) and a shown to act as scaffolds to various cationic, anionic and
viologen ditosylate salt G2TsO were constructed, among which, biologically significant guests. Among these water‐soluble
one formed from WP6 and G2+ ion can be controlled by the pillararenes, anionic ones modified with –COO groups and
+
sequential addition of an acid and a base (HCl and NaOH, cationic ones with –NH3 groups have an inherent advantage:
respectively), whereas the other fabricated from CP6 and TsO ion they are responsive to acid/base reagent pairs (such as HCl and
can be switched through the sequential addition of basic and NaOH). Based on these acid‐base responsive pillararenes,
acidic reagents (NaOH and HCl, respectively).
plenty of supramolecular systems have been reported.5h,I,6k,9a,e
Searching new guests for these negatively and positively
charged pillararenes to build acid‐base switchable host‐guest
complexation is thus very interesting. Herein, 1,1′‐bis(6‐
In the field of supramolecular chemistry, switchable
complexation has played an important role because of its wide
applications in the fabrication of various interesting and
important supramolecular systems, such as molecular switches
and machines,1 responsive supramolecular polymers,2 and
other smart materials.3 In the past decades, light irradiation,
temperature, pH, redox reagents, enzymes and other external
stimuli have been widely employed to construct various
switchable host‐guest complexation systems.4 Among these
stimuli, acid‐base response is gaining more and more attention
because it is of special interest in the applications for
information storage materials, electronic devices, and drug
delivery.5 Therefore, it is particularly important to build acid‐
base switchable host‐guest complexation systems.
aminohexyl)‐4,4′‐bipyridinium ditosylate
selected as the ion‐paired ionic guest, owing to the interesting
and well‐known15 physicochemical properties of the 4, 4
(
G
2TsO
)
was
′
‐
bipyridinium (viologen) unit. The design and construction of
acid‐base and base‐acid switchable host‐guest complexations
were elaborated in Scheme 1. We show that two different ions
of the same structurally simple ion‐paired organic salt (see
structure
G

2TsO in Scheme 1) form highly stable inclusion
complexes (G2+
⊂
WP6 supercation and TsO
⊂
CP6 superanion)
with two water‐soluble anionic pillar[6]arene (WP6) and
cationic pillar[6]arene (CP6), respectively. Based on these two
Pillararenes,6 added to the list of macrocyclic hosts in 2008,
have attracted a great deal of attention from supramolecular
chemists. Owing to their intrinsic unique rigid and symmetrical
pillar architecture and easy modification, pillararenes have
been endowed with outstanding abilities in molecular
recognition and in the construction of various interesting
supramolecular systems, such as daisy chains,7 supramolecular
polymers,8 drug‐release systems,9 transmembrane channels10
and other advanced functional materials.11 By adopting
different functionaliztion methods, anionic,12 cationic13 and
a. School of Materials and Chemical Engineering, Henan University of Engineering,
Zhengzhou, 450006, China. E‐mail:qpduan@haue.edu.cn; wf2003@haue.edu.cn
b. School of Chemical Engineering and Food Science, Zhengzhou Institute of
Technology, Zhengzhou, 450044, China. E‐mail: luckyluke@haue.edu.cn
†Electronic Supplementary Information (ESI) available: Synthetic procedures,
characterizations, NMR spectra, and the calculation of binding constant. See
DOI: 10.1039/x0xx00000x
Scheme 1 Chemical structures and cartoon representation of pillar[6]arenes WP6 and
CP6 and guest G2TsO; Illustration of the acid‐base controlled dethreading/rethreading
process.
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recognition motifs, acid/base and base/acid‐switchable
complexations were demonstrated.
, G
WP611a CP616 and 2TsO17 were prepared according to the
previous published procedures. As shown in Scheme 1, thanks
to their difference in mode of supramolecular interactions,
hosts WP6 and CP6 can selectively bind the viologen‐
containing threadlike molecule G2+ and tosylate ion (TsO
)
1
subunits of
WP6 guest
2TsO WP6 in D2O are shown in Fig. 1. As can be seen from
Fig. 1b, the proton signals of the guest
2+ ion (a‐g) exhibit an
G
2TsO, respectively. The H NMR spectra of host
,
G2TsO, and 1:2 molar ratio mixture of
G
/
G
obvious upfield shift and a broadening effect against free guest
G2+ ion proton signals. Strong upfield shifts (Δδ) of the
aromatic protons (Ha and Hb protons on the viologen subunit)
and methylene protons indicate that guest G
2+ ion is located in
Fig. 2 Partial 1H NMR spectra (400 MHz, D2O, 298 K): (a)
CP6 (3.00 mM) and 2TsO (3.00 mM); (c) after addition of 2.0 
NaOD solution (30%) to b; (d) after addition of 3.0
G

2TsO (3.00 mM); (b)
L of aqueous
L of aqueous DCl solution
the host cavity. These shifts appeared due to rather fast
G
1
proton exchange observed for complexation in the H NMR
timescale. It should be noted that Δδ (b) > Δδ (a) > Δδ (c) > Δδ
(e) > Δδ (f) > Δδ (g) > Δδ (d). Hence, the bipyridinium unit of
G2+ ion should be deeper incorporated into the cavity of the
host WP6 (Δδ = 1.28 and 1.11 ppm for b and a, repectively).
(20%) to c; (e) CP6 (3.00 mM).
the TsO ions (Fig. 1b). A Job plot (Fig. S9, ESI†) based on UV‐
vis absorption data demonstrated that WP6 and G2+ form a
complex in a 1:1 ratio in aqueous solutions. The association
constants (Ka) of the complex G2+
⊂WP6 in aqueous solutions
was determined to be (4.78 ± 0.57) × 105 M‐1 by a fluorescence
titration method (Fig. S11, ESI†).
+
Further evidence for the complexation between WP6 and G2
ion was obtained from UV−vis absorpꢀon spectroscopy. The
spectrum of an equimolar aqueous solution of WP6 and
G2TsO displays a broad absorption above 400 nm which
corresponds to the characteristic absorption of the charge‐
transfer complex between the aromatic rings of WP6 and the
bipyridinium unit of G2+ ion (Fig. S4, ESI†). In addiꢀon, a
noticeable red‐shift was observed (Fig. S5, ESI†), suggesꢀng
Furthermore, the complexation of
G
2TsO by the cationic
1
pillar[6]arene CP6 host was also examined. Similarly, H NMR
examination was also carried out to study the host‐guest
complexation between CP6 and
2b, the 1:1 mixture of CP6 and
G
G


2TsO in D2O. As shown in Fig.
2TsO in D2O had substantial
the electronic interaction between WP6 and G
2+ ion.11a The 2D
NOESY data (Fig. S6, ESI†) showed the NOE correlations
between the aromatic protons (Ha and Hb) of the entrapped
G2+ ion and the aromatic proton H1 of WP6, which also
upfield shifts and broadening effects for the TsO protons (HA‐C
)
compared to free
G2TsO (∆δ = 0.32 to 0.91 ppm) (Fig. 2a),
indicating a strong threaded host‐guest complex formation.
And the presence of only one set of peaks for the solution of
CP6 and TsO (Fig. 2b) suggests the host‐guest complex
formation is a fast exchange process on the NMR time scale.
The 2D NOESY spectrum (Fig. S7, ESI†) clearly showed the NOE
correlation signals between HA, HB or HC on TsO and protons
H1‐4 on CP6, respectively, supporting the assignment of a
confirmed the formation of the threaded complex G2+
supercation. There is no host‐guest interaction between the
TsO ions subunit of guest
2TsO and WP6 since excess WP6
caused no change in chemical shifts for the proton signals of
WP6
G
threaded structure TsO
CP6 to the D2O solution of complex TsO
obvious chemical shift changes for the proton signals of the
2+ ion (Fig. S8, ESI†), so excess CP6 did not lead to the binding
of a second CP6 by the 2TsO. A Job plot
2+ subunit of guest
⊂
CP6 superanion. Addition of excess
CP6 caused no
⊂
G
G
G
(Fig. S10, ESI†) based on fluorescence titrations data
demonstrated that CP6 and TsO ions form a 1:1 host‐guest
complex in aqueous solutions. The association constants (Ka) of
the complex TsO
⊂CP6 in aqueous solutions was determined
to be (6.65 ± 0.26) × 105 M‐1 by a fluorescence titration method
(Fig. S12, ESI†). We speculated that the highly strong
formation of the complexes between
G2TsO and the two
hosts in water might be ascribed to the cooperative
interactions of multiple electrostatic interactions, hydrophobic
Fig. 1 Partial 1H NMR spectra (400 MHz, D2O, 298 K): (a)
WP6 (6.00 mM) and 2TsO (3.00 mM); (c) after addition of 6.0 
DCl solution (20%) to b; (d) after addition of 3.0
G

2TsO (3.00 mM); (b)
L of aqueous
L of aqueous NaOD solution
interactions and π‐π stacking interactions5h,13c
.
G
Given the fact that hosts WP6 and CP6 can selectively bind
2+ and TsO subunits of
2TsO, respectively, the
(30%) to c; (e) WP6 (6.00 mM).
G
G
2 | J. Name., 2012, 00, 1‐3
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remarkably and the peaks of Ha–g became broad again by
deprotonating the carboxylate groups on both rims of WP6
upon addition of NaOD (Fig. 1d), indicating the reformation of
the complex between WP6 and
NaOD was added to the mixed solution of CP6 and
G
2+ ion. On the contrary, when
2TsO, the
G
signals of TsO ion returned to almost their uncomplexed
positions (Fig. 2c), signaling that the complexation between
CP6 and TsO ion was totally quenched. The reason is apparent:
when the solution became basic by adding an aqueous NaOD
solution, the NH3+ groups on CP6 were deprotonated to afford
the neutral amino groups, resulting in the disappearance of
the electrostatic interactions between CP6 and TsO ion.
However, after addition of DCl to this solution, an 1H NMR
spectrum similar to that of the original solution of CP6 and
TsO ion was obtained (Fig. 2d), resulting from the protonation
of the amino groups and the regeneration of the complex
between CP6 and TsO ion in this solution. Therefore, the
Fig. 3 Partial 1H NMR spectra (400 MHz, D2O, 298 K): (a) CP6 (3.00 mM); (b) WP6
(6.00 mM); (c)
(3.00 mM) + WP6 (6.00 mM); (e)
(3.00 mM); (g) 2TsO (3.00 mM) + CP6 (1.50 mM) + WP6 (1.00 mM); (h) G
G

2TsO (3.00 mM) + WP6 (6.00 mM) + CP6 (3.00 mM); (d)
2TsO (3.00 mM); (f) 2TsO (3.00 mM) + CP6
2TsO
G2TsO
G
G
host‐guest complexes G2+ WP6 supercation and TsO
⊂ ⊂CP6
G

superanion can be controlled reversibly from its complexed
state to its uncomplexed state through the addition of a
base/acid and an acid/base reagent pairs, respectively. In a
(3.00 mM) + CP6 (3.00 mM) + WP6 (3.00 mM);
simultaneous binding of the ion‐paired organic salt G2TsO by
word, the complexation between WP6 or CP6 and G2TsO is
the binary WP6
The 1H NMR spectra of
TsO
CP6, and an equimolar mixture of
CP6 in D2O are shown in Fig. 3. The signals of the hosts WP6
and CP6 disappear except for those of the guest 2TsO upon
mixing equimolar solution of 2TsO WP6 and CP6 (Fig. 3h),
suggesting that supramolecular system WP6
G2+
supercation and TsO
CP6 superanion) was not formed. The
/
CP6 host systems was thus examined in D2O
2TsO WP6 CP6 WP6
G2+
2TsO
.
,
pH‐responsive and its reversible property can be used to offer
a simple on‐off switch that is of great importance in the
construction of controllable molecular switches.
G
,
,
G
,
⊂
⊂

, WP6, and
G

G
,
Conclusions
a
(
⊂
In conclusion, we reported controllable construction of two
new host‐guest complexations based on water‐soluble anionic
pillar[6]arene WP6 or cationic pillar[6]arene CP6 with a
⊂
reason is that when WP6 was mixed with an equivalent
amount of CP6 a precipitate was formed, probably due to the
formation of water‐insoluble supramolecular complexes driven
by electrostatic interaction between WP6 and CP6. This is
viologen
bipyridinium ditosylate (
WP6 and CP6 could form a stable 1:1 inclusion complex with
their complementary ion, G2+ and TsO
respectively.
ditosylate
salt,
1,1′‐bis(6‐aminohexyl)‐4,4′‐
G
2TsO). It was demonstrated that
1
corroborated by the H NMR spectra presented in Fig. S13c.
1
,
When WP6 was in excess, only it was observed in the H NMR
Furthermore, among these two host‐guest complexations, one
formed from WP6 and G2+ ion can be switched between its
complexed and decomplexed states through the sequential
addition of an acid and a base (HCl and NaOH, respectively),
whereas the other fabricated from CP6 and TsO ion can be
operated equally through the sequential addition of basic and
acidic reagents (NaOH and and HCl, respectively). This result
enriches the field of controlled pillararene chemistry. Our
further studies will focus on expanding these new acid/base
and base/acid‐switchable complexations to fabricate
spectra (Fig. S13b, ESI†), and when CP6 was excessive only the
signals of CP6 was observed in the 1H NMR spectra (Fig. S13d,
ESI†). Excess amount of WP6 or CP6 led to the complexation of
each host towards its complementary ion (G2+ and TsO
,
1
respectively), which is substantiated by the H NMR spectra
presented in Fig. 3c and 3g, respectively.
Additionally, both the obtained G2+
TsO
CP6 superanion have pH‐responsiveness, that is to say,
⊂WP6 supercation and
⊂
the assembly and disassembly of the two inclusion complexes
can be reversibly controlled by addition of HCl and NaOH
aqueous solutions. Proton NMR studies were performed to
testify these two reversible processes (Fig. 1 and 2). Compared
with the spectra of WP6 and G2+ ion in D2O (Fig. 1b), the
signals for the protons on WP6 disappeared (Fig. 1c) after
responsive
supramolecular
polymers
and
smart
supramolecular materials in aqueous media.
Conflicts of interest
There are no conflicts to declare.
adding DCl to the mixed solution of WP6 and G2TsO due to
the formation of water‐insoluble carboxylic acid substituted
pillar[6]arene.11a Meanwhile, the chemical shifts and the split
of Ha–g on G
2+ ion migrated back to their original states as the
individual G2+ ion, suggesting that the guest G2+ ion
dethreaded from the cavity of WP6. On the other hand, the
signals corresponding to protons on G2+ ion shifted upfield
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (no. 21402040, 21572046), Henan
province science and technology research program
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Organic & Biomolecular Chemistry
View Article Online
DOI: 10.1039/C9OB00398C
Acid/base-and base/acid-switchable complexationes between
anionic-/cationic-pillar[6]arenes and a viologen ditosylate salt
Qunpeng Duan, Hongsong Zhang, Wenpeng Mai, Fei Wang and Kui Lu
Acid/base and base/acid-controllable molecular switches were constructed based on water-soluble
anionic pillar[6]arene or cationic pillar[6]arene and a viologen ditosylate salt.