Ion-controlled switchable complexation between pentiptycene-based tweezer-like hosts and self-folding guests

Article abstract of DOI:10.1016/j.tet.2013.04.030

A couple of self-folding A-D-A guests were synthesized, and it was found that the guests could be included by the pentiptycene-based tweezer-like hosts to form stable 1:1 complexes in solution, which have been evidenced by the ¹H NMR, ROESY 2D

Full text of DOI:10.1016/j.tet.2013.04.030

Accepted Manuscript
Ion-controlled switchable complexation between pentiptycene-based tweezer-like
hosts and self-folding guests
Ying Han, Jia-Bin Guo, Jing Cao, Chuan-Feng Chen
PII:
S0040-4020(13)00568-1
10.1016/j.tet.2013.04.030
TET 24230
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 7 February 2013
Revised Date: 26 March 2013
Accepted Date: 8 April 2013
Please cite this article as: Han Y, Guo J-B, Cao J, Chen C-F, Ion-controlled switchable complexation
between pentiptycene-based tweezer-like hosts and self-folding guests, Tetrahedron (2013), doi:
10.1016/j.tet.2013.04.030.
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Ion-controlled switchable complexation between
pentiptycene-based tweezer-like hosts and self-
folding guests
Ying Han,a,b Jia-Bin Guo,a Jing Caoa and Chuan-Feng Chena,*
aBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and
Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. bUniversity of Chinese
Academy of Sciences, Beijing 100049, China.

ACCEPTED MANUSCRIPT
Tetrahedron
TETRAHEDRON
Pergamon
Ion-controlled switchable complexation between pentiptycene-
based tweezer-like hosts and self-folding guests
Ying Han,a,b Jia-Bin Guo,a Jing Caoa and Chuan-Feng Chen,a,*
aBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100190, China.
bUniversity of Chinese Academy of Sciences, Beijing 100049, China.
Abstract—A couple of self-folding A-D-A guests were synthesized, and it was found that the guests could be included by the
1
pentiptycene-based tweezer-like hosts to form stable 1:1 complexes in solution, which have been evidenced by the H NMR, ROESY 2D
NMR and ESI MS spectra. Moreover, a potassium ion-controlled switchable process between the host and the self-folding guest was
further achieved. © 2013 Elsevier Science. All rights reserved
host. Consequently, tweezer-like hosts10 could be utilized
1. Introduction
for the purpose of inclusion with foldamer guests with large
structures.
In host-guest chemistry, a permanent and challenging topic
is to develop novel hosts with the capability of binding
specific substrate species strongly and selectively.1 During
the past decades, chemists have designed and synthesized
various macrocyclic hosts, including crown ethers,2
cryptands,3 calix[n]arenes,4 cucurbit[n]urils,5 and other
macrocycles.6 Undoubtedly, a new synthetic host could
often provide a lot of opportunities in molecular recognition
and self-assembly.
Recently, we found that the pentipytcene derivatives
might be utilized as useful building blocks for the design
and synthesis of novel hosts with specific structures and
properties.11 As a result, two pentiptycene-based tweezer-
like hosts 1 and 2 (Figure 1) were synthesized.12 They
showed open central cavities, and thus could form stable
complexes with tetracationic cyclobis(paraquat-p-phenylene)
(CBPQT4+) in different complexation modes.12b To further
study the complexation of these synthetic hosts with large
open cavities towards different kinds of organic guests, we
herein report the complexation between two pentiptycene-
based tweezer-like hosts 1 and 2 with self-folding A-D-A
guests 3 and 4 in solution in details. Thus, we found that
they could form 1:1 stable complexes respectively, in which
the guests with ‘S’ folding structures could all be included
On the other hand, it was known that paraquat
derivatives7 have become some of the most common guests,
and they have also been utilized for construction of
different kinds of interlocked assemblies, such as
pseudorotaxanes, rotaxanes, and catenanes. In addition, the
foldamers have attracted much attention during the past two
decades for they could not only mimic the structural
features of biological macromolecules, but are also
important in materials science.8,9 However, the applications
of the foldamers as guests in host-guest chemistry are still
very limited. It might be because that the foldamer used as a
guest is too large to complex with a classic macrocyclic
inside the central cavities of the hosts (Figure 1). Formation
1
of the complexes was all proved by the H NMR, ROESY
2D NMR, and ESI MS spectra. Moreover, it was also found
that the binding and release of the guests in the complexes
could be easily controlled by the addition and removal of
potassium ions.
———
Keywords: Pentiptycene; Complexation; Tweezer-like host; Self-folding guest; Ion-controlled.
* Corresponding author. Tel: +86-10-62588936; Fax: +86-10-62554449; E-mail: cchen@iccas.ac.cn
1

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Tetrahedron
H
H
H4
H2
H1
Hc
Hd
H5
Ha Hb
H3
H6
O
O
O
O
O
O
N+
N+
O
O
O
O
O
He
H
Hg
Hf
OR
O
RO
O
O
O
O
O
O
Hl
O
O
O
N+
N+
O
O
O
-
4PF6
Hk
3
H10
H11
H9
R = CH CH OMe
1
2
2
H7
H8
O
O
O
O
O
O
N+
N+
O
O
O
O
O
O
OR
Hj
RO
O
Hi
O
Scheme 1. Synthesis of guests 3 and 4. Reagents and
conditions: (a) K2CO3, CH3CN, reflux; (b) p-TsCl, Et3N,
DMAP, CH2Cl2, reflux; (c) (i) CH3CN, reflux; (ii) NH4PF6,
acetone.
Hh
O
O
O
O
O
O
O
N+
N+
4PF6
O
O
O
-
4
2 R = CH2CH2OMe
Figure 1. Structures and proton designations of hosts 1, 2
and guests 3, 4.
2.2 Complexation between pentiptycene-based tweezer-
like hosts and self-folding A-D-A guests in solution.
Complexation between pentiptycene-based tweezer-like
hosts and the self-folding A-D-A guests were first studied in
2. Results and discussion
1
solution by the H NMR spectroscopic method. When we
mixed the host 1 (3.0 mM) and 1.0 equiv of 3 in 1:1 (v/v)
CD3CN/CDCl3, a deep orange solution formed immediately
because of charge transfer between the electron-rich
aromatic rings of the host and the electron-poor pyridinium
2.1 Synthesis of self-folding A-D-A guests 3 and 4.
Synthesis of guests 3 and 4 is outlined in Scheme 1.
Starting from the dihydroxynaphthalene, the self-folding A-
D-A guests 3 and 4 linked by polyether chains could be
conveniently synthesized in three steps. First, the reaction
of dihydroxynaphthalene with 2-(2-(2-hydroxyethoxy)-
ethoxy)ethyl 4-methylbenzenesulfonate in CH3CN in the
presence of K2CO3 could give compound 5 or 6. Then, the
reaction of 5 or 6 and tosyl chloride in the presence of Et3N
and DMAP gave bistosylate 7 or 8, which was further
reacted with 1-(2-methoxyethyl)-4-(pyridin-4-yl)pyridinium
6 to afford the target compound 3 or 4. Compounds 3 and 4
were all characterized by the 1H NMR, 13C NMR, MS
spectra, elemental analysis, and X-ray crystal structures.
1
rings of the guest.13 As shown in Figure 2, the H NMR
spectrum of a 1:1 mixture of 1 and 3 showed only one set of
different signals from those of the separated host and guest,
which suggested that a new complex 1·3 was formed, and
the complexation between 1 and 3 was a fast exchange
process. Especially, it was found that the protons Ha, Hb, Hc
and Hd of the paraquat ring showed a upfield shift due to
the shielding effect of aromatic rings in 1, and H4 proton
signals of the host also shifted upfield. These observations
suggested that a stable complex between host 1 and guest 3
1
might be formed in solution. The H NMR spectroscopic
titrations further afforded a quantitative estimate for the
complexation between host 1 and guest 3 by monitoring the
changes of the chemical shift of the proton H4 of 1. The
results showed that 1:1 complex between 1 and 3 was
formed by a mole ratio plot. Accordingly, the apparent
association constant Ka,exp was calculated to be
0.5(±0.01)×103 M-1 by the Scatchard plot.13, 14
2

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Tetrahedron
Figure 2. Partial 1H NMR spectra (300 MHz,
CD3CN/CDCl3 = 1:1, v/v, 295K) of (a) free host 1, (b) 1 and
1.0 equiv. of 3, (c) free guest 3. [1]0 = 2.0 mM.
Figure 4. Partial 1H NMR spectra (300 MHz,
CD3CN/CDCl3 = 1:1, v/v, 295K) of (a) free host 2, (b) 2 and
1.0 equiv. of 4, (c) free guest 4. [2]0 = 2.0 mM.
Moreover, we identified all protons of pentiptycene-
based tweezer-like host 1 and the self-folding A-D-A guest
Similarly, we found that the complexation between host
2 and guest 4 was also a fast exchange process.13
Correspondingly, the protons Ha, Hb, Hc and Hd of the
paraquat ring showed an upfield shift due to the shielding
effect of aromatic rings in 2, while H4 proton signals also
shifted upfield (Figure 4). Moreover, the stoichiometry of
the complex was determined to be 1:1 by a mole ratio plot,
and the association constant Ka for the complex was
calculated to be 0.4(±0.01)×103 M-1 by the Scatchard plot.
This result was similar to the complexation between 1 and 3,
which could form 1:1 stable complex.
1
3 by the H-1H COSY spectrum.13 The 2D ROESY spectral
experiment13 of complex 1·3 was further carried out to
investigate the complexation between the host and the guest.
The results showed that the cross-peaks between protons Ha
and Hd in the bipyridinium ring of 3 and the proton Hγ in
crown ether units, H10 in R group of 1 were found (Figure
3), which suggested that the guest could thread the central
cavity of host 1 to form a 1:1 complex. Meanwhile, the
cross-peaks between protons Hk and Hl in the guest 3 and
the protons Hγ, Hβ in crown ether units, H10 in R group of 1
were also found, and we still found the cross-peaks between
the proton of guest 3 and H5, H6 in host 1. This result also
showed a stable complex formed between pentiptycene-
based tweezer-like host 1 and self-folding A-D-A guest 3.
We also tested the complexation between host 1 and
guest 4; host 2 and guest 3 in solution by the NMR
spectroscopy. The results showed that similar to the
complexation modes described above, and the self-folding
A-D-A guests 4 or 3 could also thread the central cavity of
the pentiptycene-based tweezer-like host 1 or 2, respectively,
to form 1:1 complex. Moreover, the association constants
for the complexes were all calculated by the Scatchard plot,
and the results were summarized in Table 1. It was found
that almost no obvious differences between the association
constants of the complexes were shown for the small
structural differences of the hosts and the guests.
H3
H1,4
He
H2
Hg
H5,6
HaHd
Hk,l
HbHc
Hf
ppm
3.2
3.4
3.6
3.8
4.0
4.2
H
H
,9
Table 1. Summary of the stoichiometries and association
constants of the complexes
H
H
Stoichiometry
,11
Compound
Ka [M-1]a
(H/G)
1:1
1·3
1·4
2·3
2·4
0.5(±0.01)×103
0.5(±0.01)×103
0.4(±0.01)×103
0.4(±0.01)×103
1:1
1:1
4.4
1:1
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0
ppm
a From the H NMR titration experiments in CD3CN/CDCl3
(1:1, v/v).
1
Figure 3. 1H-1H ROESY spectrum (300 MHz, CD3CN, v/v,
295 K) of 1 and 1.0 equiv. of 3. [1]0 = 2.0 mM.
3

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Tetrahedron
2.3 Conformations of self-folding A-D-A guests in the
solid state. We tried our best to obtain a single crystal
suitable for X-ray diffraction analysis.13 However after
trying several times, we didn’t obtain single crystals of the
complexes between the pentiptycene-based tweezer-like
host and the self-folding A-D-A guest. It might be due to
the flexibility of the pentiptycene-based tweezer-like hosts
so that the molecules could pack difficultly. Instead, we
obtained the crystal structures of self-folding A-D-A guests
3 and 4, which provided us an opportunity to investigate
their structures in the solid state.
First, we obtained a single crystal of guest 3 suitable for
X-ray diffraction analysis by vapor diffusion of diisopropyl
ether into a solution of 3 in CH3CN. As shown in Figure 5,
since the bipyridinium ring was an electron-dificient group,
while the naphthalene ring was an electron-rich group, π-π
interactions between them existed which could result in the
guest 3 to take a ‘S’ conformation. There still existed
multiple C-H···F hydrogen bonding interactions between the
Figure 6. Top view (a) and side view (b) of the crystal
structure of guest 4. Blue lines denote the non-covalent
interactions between the guest and PF6 counterions.
Solvent molecules and hydrogen atoms not involved in the
non-covalent interactions were omitted for clarity.
-
2.4 ESI MS studies on formation of the complexes. The
electrospray ionization (ESI) mass spectrometry was also
used to characterize the complexes between pentiptycene-
based tweezer-like hosts and self-folding A-D-A guests.13
Consequently, the strongest peak at m/z 535.57 for [1·3-
4PF6]4+, 762.25 for [1·3-3PF6]3+ and 1215.95 for [1·3-
2PF6]2+ were found by using the solution of 1 and 3 in 1:1
(v/v) chloroform and acetonitrile, which provided another
support for formation of 1:1 stable complex between host 1
and self-folding A-D-A guest 3. Similarly, formation of the
1:1 complexes between pentiptycene-based tweezer-like
hosts and self-folding A-D-A guests were also evidenced by
the ESI mass spectra, in which the strong peaks at m/z
535.50, 762.26, 1215.84, 560.55, 795.61, 1266.05, 560.54,
795.65 and 1266.05 for [1·4-4PF6]4+, [1·4-3PF6]3+, [1·4-
2PF6]2+, [2·3-4PF6]4+, [2·3-3PF6]3+, [2·3-2PF6]2+, [2·4-
4PF6]4+, [2·4-3PF6]3+ and [2·4-2PF6]2+, respectively, were all
observed.13
-
protons of the bipyridinium rings of the guests and PF6
counterions with the distances of 2.596 (a), 2.594 (b) and
2.597 Å (c), respectively, which might play an important
role in formation of the self-folding structure of the guest as
well. In addition, it was found that the two pyridinium rings
of the guest were all distorted by the dihedral angle of
40.72˚, and the plane composed by bipyridinium rings was
almost vertical to the plane of naphthalene ring.
2.5 K+ ion-controlled binding and release of the guest in
the complex. According to the previous work of our
group,15 we found that DB30C10 moieties could bind
potassium ions to form the stable complex, and the
consequent complexation of cations would introduce extra
electrostatic repellent force to the cationic organic guest
molecules and dissociate the previously formed host-guest
complex. Thus, the result made us further investigate the
potassium ion-controlled release and binding process of the
guest molecule in the complex of pentiptycene-based
tweezer-like host 1 and self-folding A-D-A guest 3 by a
series of 1H NMR experiments.
Figure 5. Top view (a) and side view (b) of the crystal
structure of guest 3. Blue lines denote the non-covalent
interactions between the guest and PF6 counterions.
Solvent molecules and hydrogen atoms not involved in the
non-covalent interactions were omitted for clarity.
-
Similarly, we also obtained the single crystal of guest 4
suitable for X-ray diffraction analysis from the CH3CN
solution of 4. As shown in Figure 6, it was found that the
guest 4 also took a ‘S’ conformation probably due to the π-π
interaction between the electron-dificient bipyridinium ring
and the electron-rich of naphthalene group. But it was
found that the plane composed by bipyridinium rings in 4
was parallel to the plane of the naphthalene ring, and the
two pyridinium rings of guest were distorted by the dihedral
angle of 18.85˚, which are different from those of molecule
3. Moreover, there also existed C-H···F hydrogen bonding
interactions between the protons of the bipyridinium rings
Figure 7. Cartoon description of the K+ ion-controlled
switchable complexation.
-
and the fluorine atoms of PF6 counterions with the
distances of 2.448 (a) and 2.310 Å (b), respectively.
4

ACCEPTED MANUSCRIPT
Tetrahedron
obtained on
a Finnigan Surveyor MSQ Plus mass
spectrometer. Elementary analyses were performed in the
Analytic Laboratory of this Institute. Flash column
chromatography was carried out with silica gel (100-200
mesh). Other reagents and solvents were purchased from
common commercial sources, and were used as received or
purified by distillation from appropriate drying agents.
Compounds 5-816-17 were prepared according to the
published procedures.
4.2. General procedure for the synthesis of 3 and 4
A mixture of naphthalene dimethylbenzenesulfonate (0.5
mmol)
and
1-(2-methoxyethyl)-[4,4'-bipyridin]-1-ium
hexafluorophosphate(V) (1.0 mmol) in CH3CN (30 mL)
was heated under reflux for 3 days, and then the solvent
was removed under reduced pressure. The residue was
dissolved in acetone, and then added a concentrated
aqueous solution of NH4PF6. After 2 h, the solvent was
removed, and the solid was washed with water to give crude
hexafluorophosphate, which was further recrystallized from
CH2Cl2 and CH3CN to give the target product.
Figure 8. Partial 1H NMR spectra (CD3CN, 300 MHz) of (a)
free guest 3, (b) 1 and 1.0 equiv. of 3, (c) to the solution of
b was added 4.0 equiv. of KPF6, and (d) to the solution of c
was added 6.0 equiv. of [18]-crown-6, [1]0 = 2.0 mM.
As shown in Figure 8c, when 4.0 equiv. of KPF6 were
added into solution of a complex 1·3, the proton signals of
the complex disappeared, while the proton signals of the
decomplexated species were observed. But when 6.0 equiv.
of 18-crown-6 ether was added into the above system, the
proton signals of complex 1·3 were recovered (Figure 8d).
Thus, the ion-controlled binding and release of guest 3 in
the complex could be easily performed by adding and
removing the potassium ions.
4.2.1. Compound 3: Yellow solid, 85% yield. Mp 175~178
1
°C. H NMR (300 MHz, acetone-d6): δ 9.36 (d, J = 6.4 Hz,
4H), 9.16 (d, J = 6.4 Hz, 4H), 8.65 (d, J = 6.3 Hz, 4H), 8.59
(d, J = 6.3 Hz, 4H), 7.61 (d, J = 8.9 Hz, 2H), 7.20 (s, 2H),
7.06 (d, J = 8.8 Hz, 2H), 5.13-5.09 (m, 4H), 5.07-4.95 (m,
4H), 4.25-4.20 (m, 8H), 4.08-3.94 (m, 4H), 3.89-3.87 (m,
4H), 3.82-3.70 (m, 8H), 3.35 (s, 6H). 13C NMR (75 MHz,
acetone-d6): δ 156.3, 150.8, 147.4, 147.1, 130.6, 129.3,
127.5, 120.0, 108.0, 100.9, 71.2, 71.1, 71.0, 70.4, 69.7, 68.5,
-
3. Conclusions
62.6, 59.1, 55.0. MALDI-TOF MS: m/z 820.7 for [M-4PF6
]4+, 965.7 for [M-3PF6 ] . Elemental analysis calcd for
- 3+
In conclusion, we have synthesized a couple of new guests
3 and 4 with the self-folding A-D-A structures, and
demonstrated that the pentiptycene-based tweezer-like hosts
1 and 2 could form 1:1 stable complexes with guests 3 and
4 in solution. The formation of the complexes was proved
C48H60F24N4O8P4·3H2O: C 39.63, H 4.57, N 3.85; found: C
40.01, H 4.36, N 3.98.
4.2.2. Compound 4: Purple solid, 11% yield. Mp 167~169
1
°C. H NMR (300 MHz, acetone-d6): δ 8.83 (d, J = 6.6 Hz,
1
by the H NMR, ROESY 2D NMR, and ESI MS spectra.
4H), 8.73 (d, J = 6.6 Hz, 4H), 8.12 (d, J = 6.3 Hz, 4H), 8.05
(d, J = 6.3 Hz, 4H), 7.47 (d, J = 8.4 Hz, 2H), 7.25 (m, 2H),
6.87 (d, J = 7.8 Hz, 2H), 4.75 (s, 8H), 4.27-4.23 (m, 4H),
4.03-3.89 (m, 12H), 3.73 (m, 8H), 3.33 (s, 6H). 13C NMR
(75 MHz, acetone-d6): δ 155.1, 150.5, 147.1, 146.8, 127.4,
127.3, 127.1, 126.9, 114.9, 107.2, 71.5, 71.1, 70.8, 70.6,
69.4, 69.1, 62.6, 62.5, 59.4. ESI MS: m/z 205.6 for [M-
Moreover, it was found that the binding and release of the
guests in the complexes could be easily controlled by the
addition and removal of potassium ions. Based on these
developed host-guest complexation, our further studies will
focus on the applications of the novel synthetic host in
molecular assembly and molecular machines, which are
now in progress.
- 4+
- 3+
- 2+
4PF6 ] , 322.4 for [M-3PF6 ] , 555.8 for [M-2PF6 ] .
Elemental analysis calcd for C48H60F24N4O8P4: C 41.15, H
4.32, N 4.00; found: C 41.06, H 4.37, N 4.11.
4. Experimental
4.1. General
4.3. CCDC 923288 (3) and CCDC 923289 (4) contain the
supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk.
Melting points, taken on an electrothermal melting point
1
apparatus, are uncorrected. H NMR and 13C NMR spectra
were recorded on a DMX300 NMR. Tetramethylsilane
(TMS) was used as an internal standard, with chemical
shifts expressed in parts per million (ppm) downfield from
the standard. MALDI-TOF mass spectra were obtained on a
BIFLEXIII mass spectrometer. ESI mass spectra were
4.3.1 Crystal data for 3: C24H30F12N2O4P2, Mw = 700.44,
crystal size 0.32 x 0.21 x 0.20 mm3, triclinic, space group
P-1, a = 8.345 (3) Å, b = 13.498 (4) Å, c = 13.974 (4) Å,
α
= 71.754 (10)° β = 84.234 (12)° γ = 76.011 (11)°, V =
5

ACCEPTED MANUSCRIPT
Tetrahedron
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Frasconi, M.; Sampath, S.; Giesner, M. A.; McGrier, P. L.;
Bruns, C. J.; Stern, C. L.; Sarjeant, A. A.; Stoddart, J. F. J. Am.
Chem. Soc. 2013, 135, 183–192. (c) Hu, S.-Z.; Chen, C.-F.
Chem. Eur. J. 2011, 17, 5424–5431. (d) Boyle, M. M.;
Forgan, R. S.; Friedman, D. C.; Gassensmith, J. J.; Stoddart, J.
F.; Sauvage, J. Chem. Commun. 2011, 47, 11870–11872. (e)
Cragg, P. J.; Sharma, K. Chem. Soc. Rev. 2012, 41, 597–607.
(f) Xue, M.; Yang, Y.; Chi, X. D.; Zhang, Z. B.; Huang, F. H.
Acc. Chem. Res. 2012, 45, 1294–1308. (g) Li, C. J.; Han, K.;
Li, J.; Zhang, H. C.; Ma, J. W.; Shu, X. Y.; Chen, Z. X.; Weng,
L. H.; Jia, X. S. Org. Lett. 2012, 14, 42–45. (h) Hu, X. Y.; Wu,
X.; Duan, Q. P.; Xiao, T. X.; Lin, C.; Wang, L. Y. Org. Lett.
2012, 14, 4826–4829. (i) Duan, Q. P.; Xia, W.; Hu, X. Y.; Ni,
M. F.; Jiang, J. L.; Lin, C.; Pan, Y.; Wang, L. Y. Chem.
Commun. 2012, 48, 8532–8534. (j) Shu, X. Y.; Chen, S. H.;
Li, J.; Chen, Z. X.; Weng, L. H.; Jia, X. S.; Li, C. J. Chem.
Commun. 2012, 48, 2967–2969.
0.262 mm-1, 12846 reflections measured, 6584 unique (Rint
= 0.0495), final R indices [I > 2σ(I)]: R1 = 0.0759, wR2 =
0.2194, R indices (all data): R1 = 0.0856, wR2 = 0.2267.
4.3.2 Crystal data for 4: C56H66F24N6O8P4·CH3CN, Mw
=
1482.99, crystal size 0.52 x 0.40 x 0.35 mm3, triclinic,
space group P-1, a = 10.789 (2) Å, b = 11.294 (2) Å, c =
13.711 (3) Å,
V = 1565.8 (5) Å3, Z = 1, Dc = 1.573 Mg/m3, T = 173(2) K,
= 0.249 mm-1, 11449 reflections measured, 5434 unique
α = 95.52 (3)° β = 108.99 (3)° γ = 93.16 (3)°,
µ
(Rint = 0.0271), final R indices [I > 2σ(I)]: R1 = 0.0431, wR2
= 0.1097, R indices (all data): R1 = 0.0458, wR2 = 0.1118.
Acknowledgments
We thank the National Natural Science Foundation of
China (20972162, 91127009), and the National Basic
Research Program (2011CB932501) for financial support.
Supplementary material
Copies of 1H and 13C NMR spectra for new compounds. 1H-
1H COSY spectra and ROESY spectra for the complexes.
Determination of the association constants. ESI-MS spectra
for the complexes. This material associated with this article
can be found, in the online version, at doi: 10.1016/j.tet.
2013.xx.xxx.
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7

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Supplementary materials
Ion-controlled switchable complexation between
pentiptycene-based tweezer-like hosts and self-folding guests
Ying Han,a,b Jia-Bin Guo,a Jing Cao,a and Chuan-Feng Chena,*
aBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular
Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing
100190, China. bUniversity of Chinese Academy of Sciences, Beijing 100049, China.
Email: cchen@iccas.ac.cn
Contents
1. Characterization data of new compounds------------------------------------------------S2
2. 1H-1H COSY and 2D ROESY NMR spectra of the complexes-----------------------S4
3. 1H NMR spectroscopic titrations of the complexes ------------------------------------S6
4. Determination of the association constants of the complexes -----------------------S10
5. ESI MS spectra of the complexes----------------------------------------------------------S16
6. Crystal data of guests------------------------------------------------------------------------ S18
7. K+ ion-controlled switchable complexation between 1 and 3------------------------ S20
S1

ACCEPTED MANUSCRIPT
1. Characterization data of new compounds
Figure S1. 1H NMR spectrum (300 MHz, acetone-d6) of 3.
Figure S2. 13C NMR spectrum (75 MHz, acetone-d6) of 3.
S2

ACCEPTED MANUSCRIPT
Figure S3. 1H NMR spectrum (300 MHz, CD3CN) of 4.
Figure S4. 13C NMR spectrum (75 MHz, CD3CN) of 4.
S3

ACCEPTED MANUSCRIPT
1
2. H-1H COSY and 2D ROESY NMR spectra of the complexes
Hg
He
H1,4
H2
H3
H
bHc
H5,6
H
aHd
Hk,l
Hf
ppm
1
2
3
4
5
6
7
8
9
9
8
7
6
5
4
3
2
1
ppm
Figure S5. 1H-1H COSY spectrum (300 MHz, CD3CN, v/v, 295 K) of 1 and 1.0 equiv.
of 3. [1]0 = 2.0 mM.
S4

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H
Ha
Hb Hc Hd
H
H
H4
H2
H1
H3
H5
O
O O
O O O
O
O
O
N+
He
N+
H6
O
O
Hg
Hf
OR
O
RO
O
O
O
O
O
O
O
O
Hl
N+
O
O
N+
Hk
O O
-
4PF6
R = CH2CH2OCH3
H
H H
1
3
H3
H1,4
He
H2
H5,6
HaHd
HbHc
Hk,l
Hg
Hf
ppm
3.2
3.4
3.6
3.8
4.0
4.2
H
H
,9
H
H ,11
4.4
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0
ppm
1
Figure S6. H-1H ROESY spectrum (300 MHz, CD3CN, v/v, 295 K) of 1 and 1.0 equiv.
of 3. [1]0 = 2.0 mM.
S5

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1
3. H NMR spectroscopic titrations of the complexes
Figure S7. Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3=1:1, v/v, 295K) of (a) free
host 1, (b) 1 and 1.0 equiv. of 3, (c) free guest 3. [1]0 = 2.0 mM.
S6

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Ha
Hb Hc Hd
N+
H4
H2
H1
H3
H5
O O
O O O
O
O
O
H6
O
N+
O
O
OR
O
Hj
RO
O
Hi
O
O
Hh
N+
O
O
O
O
O
O
O O
O
N+
-
R = CH2CH2OMe
4PF6
4
1
Figure S8. Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3=1:1, v/v, 295K) of (a) free
host 1, (b) 1 and 1.0 equiv. of 4, (c) free guest 4. [1]0 = 2.0 mM.
S7

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Ha
N+
Hb Hc Hd
N+
H4
H2
H1
H5 H7
H3
O
O O
O O O
O
O
O
H8
O
O
He
Hg
Hf
OR
O
RO
O
O
O
O
O
O
O
O
O
O O
O
N+
N+
-
4PF6
R = CH2CH2OMe
2
3
(c)
(b)
(a)
Hf
Ha Hd
Hb Hc
H
g He
H4
H5,7
H1,8
H3
Hf
Hg
H2
Hc
Hb
Ha
Hd
H4 H5
H3
H1,8
H2
H7
Figure S9. Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3=1:1, v/v, 295K) of (a) free
host 2, (b) 2 and 1.0 equiv. of 3, (c) free guest 3. [2]0 = 2.0 mM.
S8

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1
Figure S10. Partial H NMR spectra (300 MHz, CD3CN/CDCl3=1:1, v/v, 295K) of (a)
free host 2, (b) 2 and 1.0 equiv. of 4, (c) free guest 4. [2]0 = 2.0 mM.
S9

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4. Determination of the association constants of the complexes
2.5
2.0
1.5
1.0
0.5
0.0
2
R = 0.990
2
R = 0.997
6.820 6.825 6.830 6.835 6.840 6.845 6.850 6.855
Chemical shift of H on Host (ppm)
5
Figure S11. Mole ratio plot for the complexation between 1 and 3 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [1]0 = 2.0 mM.
0.040
0.038
0.036
2
R = 0.984
0.034
0.032
0.030
Y = 0.05-0.07X
0.028
 = 0.052
0
0.026
0.024
0.20
0.25
0.30
1/[3]
0.35
0.40
0.45
0
Figure S12. Determination of Δ0 of H4 for the complexation between 1 and 3 in
CD3CN/CDCl3 (1:1, v:v) at 295 K. [1]0 = 2.0 mM.
S10

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340
320
300
280
260
240
220
2
R = 0.993
Y = 538.7-415.5X
-1
3
K = 0.5(0.01)10 M
a
0.45
0.50
0.55
0.60
0.65
0.70
0.75
p
Figure S13. Scatchard plot for the complexation between 1 and 3 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [1]0 = 2.0 mM.
2.5
2.0
2
R = 0.992
1.5
1.0
2
R = 0.987
0.5
0.0
6.92
6.93
6.94
6.95
6.96
6.97
6.98
Chemical shift of H on Host (ppm)
5
Figure S14. Mole ratio plot for the complexation between 1 and 4 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [1]0 = 2.0 mM.
S11

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0.064
0.060
0.056
0.052
0.048
0.044
2
R = 0.978
Y = 0.086-0.11X

= 0.09
0
0.20 0.22 0.24 0.26 0.28 0.30 0.32 0.34 0.36
1/[4]
0
Figure S15. Determination of Δ0 of H4 for the complexation between 1 and 4 in
CD3CN/CDCl3 (1:1, v:v) at 295 K. [1]0 = 2.0 mM.
300
280
260
2
R = 0.960
Y = 509-401X
240
-1
3
K = 0.5(0.01)10 M
a
220
0.50
0.55
0.60
0.65
0.70
0.75
p
Figure S16. Scatchard plot for the complexation between 1 and 4 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [1]0 = 2.0 mM.
S12

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2.5
2.0
1.5
1.0
0.5
2
R = 0.993
2
R = 0.992
6.965
6.970
6.975
6.980
6.985
Chemical shift of H on Host (ppm)
5
Figure S17. Mole ratio plot for the complexation between 2 and 3 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [2]0 = 2.0 mM.
0.030
0.028
0.026
2
R = 0.979
0.024
0.022
Y = 0.04-0.05X
 = 0.04
0
0.020
0.018
0.20
0.25
0.30
0.35
0.40
0.45
1/[3]
0
Figure S18. Determination of Δ0 of H4 for the complexation between 2 and 3 in
CD3CN/CDCl3 (1:1, v:v) at 295 K. [2]0 = 2.0 mM.
S13

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320
300
280
260
240
220
2
R = 0.973
Y = 448-301X
-1
3
K = 0.4(0.01)10 M
a
0.45
0.50
0.55
0.60
0.65
0.70
0.75
p
Figure S19. Scatchard plot for the complexation between 2 and 3 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [2]0 = 2.0 mM.
2.5
2.0
2
R = 0.978
1.5
1.0
2
R = 0.997
0.5
0.0
6.930 6.937 6.944 6.951 6.958 6.965 6.972
Chemical shift of H on Host (ppm)
5
Figure S20. Mole ratio plot for the complexation between 2 and 4 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [2]0 = 2.0 mM.
S14

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0.048
0.044
0.040
0.036
0.032
0.028
2
R = 0.993
Y = 0.063-0.085X

= 0.06
0
0.20
0.25
0.30
1/[4]
0.35
0.40
0.45
0
Figure S21. Determination of Δ0 of H4 for the complexation between 2 and 4 in
CD3CN/CDCl3 (1:1, v:v) at 295 K. [2]0 = 2.0 mM.
300
285
270
255
2
R = 0.971
Y = 473-344X
240
-1
3
K = 0.4(0.01)10 M
a
225
210
0.50
0.55
0.60
0.65
0.70
0.75
p
Figure S22. Scatchard plot for the complexation between 2 and 4 in CD3CN/CDCl3 (1:1,
v:v) at 295 K. [2]0 = 2.0 mM.
S15

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5. ESI MS spectra of the complexes
hy-c1+g #10-23 RT: 0.16-0.38 AV: 14 NL: 1.78E6
T: {0,0} + c ESIcorona sid=30.00 det=1188.00 Full ms [ 200.00-2000.00]
555.85
100
[3-2PF6]2+
4+
90
80
70
60
50
40
30
20
10
0
.
[1 3-4PF6]
535.57
762.25
3+
.
[1 3-3PF6]
2+
.
[1 3-2PF6]
1215.95
1256.60
513.59
732.98
680.54
822.22
800
1171.80
1049.12
1000
1371.07 1541.71 1669.94 1807.25 1916.45
400
600
1200
m/z
1400
1600
1800
2000
Figure S23. ESI MS of a solution of 1 and 3 in acetonitrile-chloroform (1:1, v:v).
hy-c1+h #14-27 RT: 0.23-0.45 AV: 14 NL: 2.45E6
T: {0,0} + c ESIcorona sid=30.00 det=1188.00 Full ms [ 200.00-2000.00]
535.50
100
4+
.
[1 4-4PF6]
90
[4-2PF6]2+
80
70
555.82
762.26
60
3+
.
[1 4-3PF6]
50
40
30
2+
.
20
[1 4-2PF6]
10
1215.84
1256.57
580.54
600
513.46
865.52
1172.57
1049.27
1000
1379.76
1400
1642.80 1724.83
1878.18
0
400
800
1200
m/z
1600 1800
2000
Figure S24. ESI MS of a solution of 1 and 4 in acetonitrile-chloroform (1:1, v:v).
S16

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hy-c2+g #13-25 RT: 0.21-0.42 AV: 13 NL: 3.64E6
T: {0,0} + c ESIcorona sid=30.00 det=1188.00 Full ms [ 200.00-2000.00]
560.55
100
4+
.
[2 3-4PF6]
90
80
70
60
50
40
3+
.
[2 3-3PF6]
30
795.61
20
2+
.
[2 3-2PF6]
511.32
492.15
10
0
584.84
600
704.18
1266.05
1442.88
1400
839.06
800
1128.71
1200
m/z
984.59
1000
1652.77 1736.87 1838.78 1967.34
400
1600
1800
2000
Figure S25. ESI MS of a solution of 2 and 3 in acetonitrile-chloroform (1:1, v:v).
hy-c2+h #13-27 RT: 0.21-0.45 AV: 15 NL: 2.36E6
T: {0,0} + c ESIcorona sid=30.00 det=1188.00 Full ms [ 200.00-2000.00]
560.54
100
90
80
70
60
50
40
30
795.65
20
10
0
584.84
600
511.32
492.12
730.64
1266.05
1437.96
839.24
800
1163.68
1200
m/z
984.92
1000
1514.16
1600
1736.34 1894.10 1967.73
400
1400
1800
2000
Figure S26. ESI MS of a solution of 2 and 4 in acetonitrile-chloroform (1:1, v:v).
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6. Crystal data of guests
Table S1. Crystal data for 3
Identification code
Empirical formula
Formula weight
Temperature
mx938
C24H30F12N2O4P2
700.44
173(2) K
Wavelength
0.71073 Å
Crystal system, space group
Unit cell dimensions
Triclinic, P-1
a = 8.345(3) Å alpha = 71.754(10)˚
b = 13.498(4) Å beta = 84.234(12)˚
c = 13.974(4) Å gamma = 76.011(11)˚
1450.0(7) Å3
Volume
Z, Calculated density
Absorption coefficient
F(000)
2, 1.604 Mg/m3
0.262 mm-1
716
Crystal size
0.32 x 0.21 x 0.20 mm
1.53 to 27.49˚
Theta range for data collection
Limiting indices
-10<=h<=10, -17<=k<=17, -18<=l<=18
12846/6584 [R(int)=0.0495]
99.0 %
Reflections collected / unique
Completeness to theta = 25.35
Absorption correction
Max. and min. transmission
Refinement method
Semi-empirical from equivalents
0.9494 and 0.9208
Full-matrix least-squares on F2
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
6584/0/397
1.552
R1 = 0.0759, wR2 = 0.2194
R1 = 0.0856, wR2 = 0.2267
1.179 and -0.805 e.Å-3
Largest diff. peak and hole
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Table S2. Crystal data for 4
Identification code
Empirical formula
Formula weight
Temperature
a
C56H66F24N6O8P4
1482.99
173(2) K
Wavelength
0.71073 Å
Crystal system, space group
Unit cell dimensions
Triclinic, P-1
a = 10.789(2) Å alpha = 95.52(3)˚
b = 11.294(2) Å beta = 108.99(3)˚
c = 13.711(3) Å gamma = 93.16(3)˚
1565.8(5) Å3
Volume
Z, Calculated density
Absorption coefficient
F(000)
1, 1.573 Mg/m3
0.249 mm-1
760
Crystal size
0.52 x 0.40 x 0.35 mm
2.55 to 25.00˚
Theta range for data collection
Limiting indices
-12<=h<=12, -10<=k<=13, -16<=l<=16
11449/5434 [R(int)=0.0271]
98.8 %
Reflections collected / unique
Completeness to theta = 25.35
Absorption correction
Max. and min. transmission
Refinement method
Semi-empirical from equivalents
1.0000 and 0.8019
Full-matrix least-squares on F2
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
5434/0/426
1.099
R1 = 0.0431, wR2 = 0.1097
R1 = 0.0458, wR2 = 0.1118
0.404 and -0.329 e.Å-3
Largest diff. peak and hole
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7. K+ ion-controlled switchable complexation between 1 and 3
Figure S27. Partial 1H NMR spectra (CD3CN, 300 MHz) of (a) free guest 3, (b) 1 and 1.0
equiv. of 3, (c) to the solution of b was added 4.0 equiv. of KPF6, and (d) to the solution
of c was added 6.0 equiv. of [18]-crown-6, [1]0 = 2.0 mM.
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