Complexation of 2,6-helic[6]arene and its derivatives with 1,1′-dimethyl-4,4′-bipyridinium salts and protonated 4,4'-bipyridinium salts: An acid-base controllable complexation

Article abstract of DOI:10.3762/bjoc.15.173

2,6-Helic[6]arene and its derivatives were synthesized, and their complexation with 1,1′-dimethyl-4,4′-bipyridinium and protonated 4,4'-bipyridinium salts were investigated in detail. It was found that the helic[6]arene and its derivatives could all form 1:1 complexes with both 1,1′-dimethyl-4,4'-bipyridinium salts and protonated 4,4'-bipyridinium salts in solution and in the solid state. Especially, the helic[6]arene and its derivatives containing 2-hydroxyethoxy or 2-methoxyethoxy groups exhibited stronger complexation with the guests than the other helic[6]arene derivatives for the additional multiple hydrogen bonding interactions between the hosts and the guests, which were evidenced by ¹H NMR titrations, X-ray crystal structures and DFT calculations. Moreover, it was also found that the association constants (K_a) of the complexes could be significantly enhanced with larger counteranions of the guests and in less polar solvents. Furthermore, the switchable complexation between the helic[6]arene and protonated 4,4'-bipyridinium salt could be efficiently controlled by acids and bases.

Full text of DOI:10.3762/bjoc.15.173

Complexation of 2,6-helic[6]arene and its derivatives with
1
4
,1′-dimethyl-4,4′-bipyridinium salts and protonated
,4'-bipyridinium salts: an acid–base
controllable complexation
Jing Li1,2, Qiang Shi1,2, Ying Han*1,2 and Chuan-Feng Chen*1,2
Full Research Paper
Open Access
Address:
Beijing National Laboratory for Molecular Sciences, CAS Key
Beilstein J. Org. Chem. 2019, 15, 1795–1804.
doi:10.3762/bjoc.15.173
1
Laboratory of Molecular Recognition and Function, Institute of
Chemistry, Chinese Academy of Sciences, Beijing 100190, China and
Received: 25 April 2019
Accepted: 18 July 2019
Published: 26 July 2019
2
University of Chinese Academy of Sciences, Beijing 100049, China
Email:
Ying Han* - hanying463@iccas.ac.cn; Chuan-Feng Chen* -
cchen@iccas.ac.cn
This article is part of the thematic issue "Novel macrocycles – and old
ones doing new tricks".
*
Corresponding author
Guest Editor: W. Jiang
Keywords:
,4'-bipyridinium salts; complexation; helic[6]arene; hydrogen bond;
© 2019 Li et al.; licensee Beilstein-Institut.
License and terms: see end of document.
4
macrocycles; macrocyclic arene
Abstract
2
,6-Helic[6]arene and its derivatives were synthesized, and their complexation with 1,1′-dimethyl-4,4′-bipyridinium and proto-
nated 4,4'-bipyridinium salts were investigated in detail. It was found that the helic[6]arene and its derivatives could all form 1:1
complexes with both 1,1′-dimethyl-4,4'-bipyridinium salts and protonated 4,4'-bipyridinium salts in solution and in the solid state.
Especially, the helic[6]arene and its derivatives containing 2-hydroxyethoxy or 2-methoxyethoxy groups exhibited stronger com-
plexation with the guests than the other helic[6]arene derivatives for the additional multiple hydrogen bonding interactions be-
tween the hosts and the guests, which were evidenced by 1H NMR titrations, X-ray crystal structures and DFT calculations. More-
over, it was also found that the association constants (Ka) of the complexes could be significantly enhanced with larger counteran-
ions of the guests and in less polar solvents. Furthermore, the switchable complexation between the helic[6]arene and protonated
4
,4'-bipyridinium salt could be efficiently controlled by acids and bases.
Introduction
Macrocyclic host molecules [1,2] play a significant role in over, cyclic structures are also the epitome of complex-binding
host–guest chemistry. Compared with noncyclic molecules, the pockets of enzymes [3]. Macrocyclic arenes including calix-
structures of macrocyclic hosts can greatly enhance the arenes [4,5], resorcinarenes [6], cyclotriveratrylenes [7,8],
host–guest complexation ability through preorganization. More- pillararenes [9], biphen[n]arenes [10] and others [11,12] are all
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composed of hydroxy-substituted aromatic rings bridged by 4,4'-bipyridinium salt could be efficiently controlled by acids
methylene or methenyl groups. They have been a kind of im- and bases.
portant macrocyclic host molecules during the last decades due
to their unique structures and a wide range of applications in
Results and Discussion
host–guest chemistry [13-18], self-assembly [19], biomedicine Synthesis of the hosts and the guests
[
20] and materials science [21,22]. The derivatives of macro- 2,6-Helic[6]arene H1 and its methyl-substituted derivative H2
cyclic arenes with diverse functional groups are also important were prepared according to previously reported methods [30].
for the development of various new host–guest supramolecular Starting from helic[6]arene H1, helic[6]arene derivatives H3
systems [23-29].
and H4 were conveniently synthesized by etherification of H1
with bromobutane or 2-bromoethyl methyl ether, respectively,
Helic[6]arenes [30], a new kind of macrocyclic arenes, are in tetrahydrofuran in the presence of sodium hydride.
composed of 2,6-dihydroxy-substituted triptycene subunits Helic[6]arene derivative H5 was synthesized by treatment of
bridged by methylene groups. They have exhibited wide poten- H1 with methyl bromoacetate followed by reduction with lithi-
tial applications in supramolecular chemistry [31-36] for their um aluminium hydride (Scheme 1). The guests G1–3 were pre-
unique structures and electron-rich cavities. In this paper, we pared according to previously reported procedures [37-39].
report the complexation between 2,6-helic[6]arene and its four Guest G4 was synthesized through reaction of 4,4′-bipyridine
derivatives with 1,1′-dimethyl-4,4′-bipyridinium and proto- with concentrated HCl in acetonitrile followed by counteranion
nated 4,4'-bipyridinium salts (Figure 1) in both solution and in exchange with sodium tetrakis[3,5-di(trifluoromethyl)phenyl]-
the solid state. We found that the helic[6]arene and its deriva- borate (NaBArF) in dichloromethane. The new compounds
tives containing 2-hydroxyethoxy or 2-methoxyethoxy groups were confirmed by NMR spectroscopy and high-resolution
showed stronger complexation with the guests than the other mass spectrometry (Supporting Information File 1, Figures
helic[6]arene derivatives. This result can be explained by the S1–S8).
additional multiple hydrogen-bonding interactions between the
hosts and the guests, which were evidenced by 1H NMR titra- Host–guest complexation in solution
tion, X-ray crystal structures and DFT calculations. Moreover, Firstly, we tested the complexation between hosts H1 and H4
we also found that the Ka values of the complexes could be sig- with guest G1 in solution by 1H NMR spectroscopy. As shown
nificantly enhanced with larger counteranions of the guests and in Figure 2, when mixing equivalent amounts of host and guest
in less polar solvent. Furthermore, the controllable complex- in CDCl3/acetone-d6 1:2 (v/v), the 1H NMR spectrum showed a
ation between (O-methyl)6-2,6-helic[6]arene and protonated new set of proton signals, which was different from the free
Figure 1: Structures and proton designations of hosts H1–5 and guests G1–4.
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Scheme 1: Synthesis of hosts H3–5.
Figure 2: Partial 1H NMR spectra (400 MHz CDCl3/acetone-d6 1:2 (v/v), 298 K) of (a) free H1, (b) H1 with 1.0 equiv G1, (c) free G1, (d) H4 with
.0 equiv G1, (e) free H4. [H1]0 = [H4]0 = [G1]0 = 2.0 mM.
1
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host or guest, indicating the formation of new complexes bipyridinium unit of G4 and the benzene ring of the hosts might
H1·G1 and H4·G1, respectively, and the complexation was a exist. The signals for protons 2 and 13 of H4 showed a down-
fast exchange process on the NMR time scale. The proton field shift with broadened signals due to deshielding effect,
signals of a and c of the bipyridinium ring showed upfield while the signals for protons 11 and 12 showed upfield shifts,
shifts, while the signal for protons b completely disappeared possibly due to hydrogen bonding between the hydrogen of the
due to the shielding effect of the aromatic rings in hosts H1 or bipyridinium unit of G4 and the oxygen atoms of the host.
H4. The signals for the protons 2, 3, and 4 of H1 and 2, 3, 4, Similarly, the complexation between other helic[6]arene deriva-
and 13 of H4 all showed downfield shifts, which might be attri- tives (H2, H3, H5) with guests G3 and G4 could also be ob-
buted to the deshielding effect of guest G1. Other helic[6]arene served (Supporting Information File 1, Figures S15–S22).
derivatives (H2, H3, H5) with guests G1 and G2 showed simi- Furthermore, job plots showed that throughout 1:1 host–guest
lar complexation as described above (Supporting Information complexes are formed (Supporting Information File 1, Figures
File 1, Figures S9–S14).
S56–S88).
We also investigated the complexation between hosts H1 and To gain quantitative insight into the complexation between the
H4 with guest G4 in solution by 1H NMR spectroscopy. As hosts and the guests, we carried out 1H NMR titrations and
shown in Figure 3, upon mixing equal equivalents of host and calculated the association constants Ka by the nonlinear curve-
guest in CD2Cl2, the 1H NMR spectrum also showed a new set fitting method [40]. As shown in Table 1, compared with
of proton signals, which was different from the free host or its derivatives, the unsubstituted host helic[6]arene H1
guest. These results indicated that the new complexes H1·G4 showed the strongest complexation with all guests tested.
and H4·G4 were formed, and the complexation between the The association constant (Ka) of complex H1·G1 was calcu-
host and the guest was a fast exchange process on the NMR lated to be (6.76 ± 1.02) ꢀ 103 M−1, while the Ka of H2·G1
time scale as well. The signal for protons d of the 4,4'-bipyri- was much lower (1.03 ± 0.15) ꢀ 102 M−1). For (O-2-
dinium ring showed an upfield shift and that for protons e com- methoxyethoxy)6-2,6-helic[6]arene H4 and (O-2-hydroxy-
pletely disappeared possibly due to the shielding effect of the ethoxy)6-2,6-helic[6]arene H5, the association constants of their
aromatic rings in H1 or H4. The proton signals of 2 and 3 of H1 complexes with G1 were found to be (1.36 ± 0.17) ꢀ 103 M−1
and 3 of H4 all showed upfield shifts with broadened peaks, and (3.10 ± 0.30) ꢀ 103 M−1, respectively, which are only
which indicated that π–π stacking interactions between the slightly smaller than that of H1·G1, but much higher than that
Figure 3: Partial 1H NMR spectra (400 MHz, CD2Cl2, 298 K) of (a) free H1, (b) H1 with 1.0 equiv G4, (c) free G4, (d) H4 with 1.0 equiv G4, (e) free
H4. [H1]0 = [H4]0 = [G4]0 = 2.0 mM.
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Table 1: Association constants (Ka) for 1:1 host–guest complexes in CDCl3/acetone-d6 1:2 (v/v) at 298 K.
Complexes
Ka [M−1]
Complexes
Ka [M−1]
H1·G1
H2·G1
H3·G1
H4·G1
H5·G1
H1·G2
H2·G2
H3·G2
H4·G2
H5·G2
(6.76 ± 1.02) ꢀ 103
(1.03 ± 0.15) ꢀ 102
–a
(1.36 ± 0.17) ꢀ 103
(3.10 ± 0.30) ꢀ 103
(1.22 ± 0.17) ꢀ 104
(1.26 ± 0.16) ꢀ 102
–a
H1·G3
H2·G3
H3·G3
H4·G3
H5·G3
H1·G4
H2·G4
H3·G4
H4·G4
H5·G4
(1.28 ± 0.17) ꢀ 102
–a
–a
(73.33 ± 8.09)
(88.72 ± 0.96)
(7.26 ± 0.93) ꢀ 103
–a
–a
(2.72 ± 0.39) ꢀ 103
(3.50 ± 0.48) ꢀ 103
(2.27 ± 0.31) ꢀ 103
(3.04 ± 0.02) ꢀ 103
aKa values not calculated due to too small binding.
of H2·G1. In the case of H3 containing n-butoxy groups, almost the 1:1 host–guest complexes were about 103 M−1 except for
no binding affinity toward G1 was observed under these condi- H2 that showed very low complexation ability with G4. When
tions.
the 1H NMR titrations were carried out in CD2Cl2, the Ka
values of complexes H1·G4, H3·G4 and H4·G4 were all higher
Compared with G1, the protonated 4,4'-bipyridinium salt G3 than 104 M−1, while the Ka value of complex H2·G4 was found
showed similar complexation behavior but significantly lower to be (6.07 ± 0.08) ꢀ 102 M−1. These results suggest that, com-
binding abilities with helic[6]arene H1 and its derivatives pared with the non-polar solvent, acetone hampers or competes
H2–5.
the intermolecular non-covalent interactions between the hosts
and the guests, and thus resulted in a decrease of the host–guest
It is known that ion-pairing effects can hamper the complex- complexation.
ation of charged species [41-43], and thus affect the host–guest
ESIMS studies of the formation of host–guest
complexation [10,44,45]. Consequently, we also prepared the
,4'-bipyridinium salts G2 and G4 with BArF− as the coun- complexes
4
teranion. As shown in Table 1, compared with guests G1 and The electrospray ionization (ESI) mass spectra also confirmed
G3 with PF6− as the counteranion, G2 and G4 exhibited higher the formation of 1:1 complexes between the hosts and the
binding abilities with the hosts probably due to a weakened ion- guests. By using a solution of H1 and G1 in chloroform/ace-
pairing effect. Especially, for complex H1·G2, the Ka value was tone 1:2 (v/v), the strongest peak at m/z 540.2056 correspond-
high (1.22 ± 0.17) ꢀ 104 M−1.
ing to [H1·G1−2PF6]2+ was found, which was in accordance
with the 1:1 complex formed in solution. Similarly, the
Solvents with different polarity can also affect the complex- strongest peaks at m/z 582.2526, 714.8325, 672.2842, 540.2061,
ation between the hosts and the guests. As shown in Table 2, we 582.2522, 714.8319, 672.2836, 526.1895, 700.3148, 658.2689,
found that performing the 1H NMR titrations of the host–guest 526.1898, 568.2365, 700.3143, 658.2681 corresponding to
complexation in CDCl3/acetone-d6 1:2 (v/v), the Ka values of [H2·G1−2PF6]2+, [H4·G1−2PF6]2+, [H5·G1−2PF6]2+,
[
[
H1·G2−2BArF]2+, [H2·G2−2BArF]2+, [H4·G2−2BArF]2+,
H5·G2−2BArF]2+, [H1·G3−2PF6]2+, [H4·G3−2PF6]2+,
Table 2: Association constants (Ka) for the 1:1 host–guest complexes
in different solvents at 298 K.
[H5·G3−2PF6]2+, [H1·G4−2BArF]2+, [H2·G4−2BArF]2+,
H4·G4−2BArF]2+, [H5·G4−2BArF]2+ were observed, which
[
Complexes Ka [M−1]
further confirmed the formation of the 1:1 host–guest com-
plexes (Supporting Information File 1, Figures S41–S55).
in CDCl3/acetone-d6
:2 (v/v)
in CD2Cl2
1
Host–guest complexation in the solid state
The single crystal of complex H1·G1 was obtained by vapor
diffusion of isopropyl ether into acetone. As shown in Figure 4,
G1 was encapsulated in the cavity of H1 to form a 1:1 complex,
in which G1 is distorted by the dihedral angle between the pyri-
dinium rings of 33.19°. There exist multiple CH···π interactions
H1·G4
H2·G4
H4·G4
H5·G4
(7.26 ± 0.93) ꢀ 103
–a
(2.27 ± 0.31) ꢀ 103
(3.04 ± 0.02) ꢀ 103
(2.11 ± 0.28) ꢀ 104
(6.07 ± 0.08) ꢀ 102
(1.13 ± 0.15) ꢀ 104
(1.92 ± 0.21) ꢀ 104
aKa value not calculated due to too small binding.
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Figure 4: Crystal structure of complex H1·G1. (a) Top view, (b) side view, and (c) packing viewed along c-axis. Blue lines denote the non-covalent
interactions between H1 and G1. Solvent molecules and hydrogen atoms not involved in the non-covalent interactions were omitted for clarity.
between the protons of G1 and the aromatic rings of H1 with tained a single crystal of H3 instead of the host–guest complex.
distances of 2.683 for A, 2.845 for B, 2.788 for C, 2.802 for D, The steric hindrance of the n-butoxy groups in H3 (Supporting
and 2.868 Å for E, respectively. There also exist π–π stacking Information File 1, Figure S90) might lead to weak complex-
interactions between the pyridinium of G1 and the aromatic ation of H3 with the tested guests in solution. However, we ob-
ring of H1 with the distance of 3.854 Å for F, a CH···O hydro- tained a single crystal of complex H5·G1 by vapor diffusion of
gen bond between the proton of G1 and oxygen of H1 in the isopropyl ether into an acetone solution. As shown in Figure 5,
distance of 2.683 Å for G. Moreover, C-H···F hydrogen bonds we found that G1 was encapsulated in the cavity of H5 to form
between the two adjacent guests with the distances of 2.670 a 1:1 complex, and the complex molecules are stacked into infi-
(
H), 2.570 (I), 2.594 (J) and 1.981 Å (K), respectively, were ob- nite channels along the a-axis (Figure 5c), which is different
served. These multiple interactions play an important role in the from that of H1·G1. There exist multiple CH···π interactions be-
formation of the host–guest complex. Furthermore, it was found tween the proton of G1 and the aromatic ring of H5 with dis-
that adjacent complexes were nearly perpendicular to each tances of 2.892 (A), 2.844 (B), 2.893 (C) and 2.853 Å (D), re-
other, which self-assembled into rhombuses with hollows along spectively. A CH···π interaction between the proton of H5 and
the c-axis (Figure 4c) and curved ribbons along the a- and the aromatic ring of G1 with a distance of 2.860 Å, and the
b-axes (Supporting Information File 1, Figure S89).
CH···π interaction between the proton of H5 and the aromatic
ring of adjacent H5 in the distance of 2.801 (F), 2.714 (G) and
By vapor diffusion of isopropyl ether into a chloroform/acetone 2.887 Å (H), respectively, are also observed. Moreover, there
:1 (v/v) solution of the 1:1 mixture of H3 and G1, we only ob- are multiple CH···O hydrogen-bonding interactions between the
1
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Figure 5: Crystal structure of complex H5·G1. (a) Top view, (b) side view, and (c) packing viewed along the a-axis. Blue lines denote the non-cova-
lent interactions between H5 and G1. Solvent molecules, PF6− counteranions and hydrogen atoms not involved in the non-covalent interactions were
omitted for clarity.
protons of G1 and the oxygen of H5 with the distances of 2.600 host. There are C–H···π interactions between the protons on the
(
(
I), 2.456 (J), 2.556 (K), 2.296 (L), 2.464 (M), 2.401 (N), 2.176 pyridinium ring of G3 and the benzene rings encompassing the
O), 2.511 (P) and 2.547 Å (Q), respectively, and OH···O cavity of H4, and C–H···O hydrogen bonding between the
hydrogen bonding between the proton of the side chain of H5
and oxygen of the side chain of adjacent H5 in the distance of
1
.989 Å (R). In addition, C-H···F hydrogen bonds between the
two adjacent guests with the distance of 2.420 (S), 2.474 (T)
and 2.187 Å (U), respectively, are observed as well. These
multiple intermolecular hydrogen-bonding interactions be-
tween the host and the guest might be the main reason for the
formation of the stable complex H5·G1.
DFT calculation of host–guest complexes
To further investigate the complexation mode and structural
characteristics of the host–guest complexes, DFT calculations
were carried out at the B3LYP/6-31G level of theory for com-
plex H4·G1 (Supporting Information File 1, Figure S92). The
calculation results revealed the C–H···π interactions between the
protons on the pyridinium ring of G1 and the benzene ring units
of the host H4 and C–H···O hydrogen bonds between the
protons of the methyl group and pyridinium rings of G1 and the
oxygen atom of H4 with distances ranging from 2.052 to
2
.769 Å. Likewise, DFT calculations at the B3LYP/6-31G level
of theory for the complexes H4·G3 and H5·G3 were also per-
formed. As shown in Figure 6, in the optimized structure, the
pyridinium ring of the guest is surrounded by the cavity of the
Figure 6: Calculated structures of the complexes at the B3LYP/6-31G
level of theory. (a) Top view and (b) side view of H4·G3, and (c) top
view and (d) side view of H5·G3.
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Beilstein J. Org. Chem. 2019, 15, 1795–1804.
Acid–base controlled complexation between
protons of the pyridinium ring of G3 and the oxygen atom of
H4 with distances ranging from 2.052 to 2.769 Å. Similar to H2 and G4
H4·G3, complex H5·G3 also shows the multiple intermolecu- 4,4′-Bipyridine easily forms protonated 4,4′-pyridinium salts
lar non-covalent interactions with distances ranging from 1.651 and vice versa. Hence we could conveniently control the associ-
to 2.575 Å.
ation and dissociation of the host–guest complexes based on
protonated 4,4′-pyridinium guests by use of acid and base. As
Compared with hosts H2 and H3, helic[6]arene H1 and its de- shown in Figure 7, when 2.2 equiv of DBU were added into the
rivatives H4 and H5 all show multiple hydrogen-bonding inter- solution of complex H2·G4 in CD2Cl2, the signals for protons 3
actions with the examined guests, which were confirmed by not and 6 of complex H2·G4 disappeared while the proton signals
only X-ray crystal structures of the complexes but also by DFT of free H2 and 4,4'-bipyridine were observed, which indicated
calculations. These additional multiple hydrogen-bonding inter- that the complex dissociated. On the other hand, when 2.2 equiv
actions might be responsible that H1 and its derivatives H4 and of TFA were added into the above solution, the proton signals
H5 show stronger host–guest complexation with the tested of the free 4,4'-bipyridine and the signals for protons 3 and 6 of
guests than those of H2 and H3. This is consistent with the free H2 disappeared, while the proton signals of complex
results obtained in solution.
H2·G4 appeared again, thus indicating the regeneration of the
Figure 7: Schematic representation of the acid–base controlled complexation process and partial 1H NMR spectra (300 MHz, CD2Cl2, 298 K) of (a)
free H2, (b) to the solution of complex H2·G4 were added 2.2 equiv of DBU, (c) to the solution of b were added 2.2 equiv of TFA, and (d) free 4,4'-
bipyridine. [H2]0 = 2.0 mM.
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Beilstein J. Org. Chem. 2019, 15, 1795–1804.
host–guest complex. Therefore, the switchable complexation ORCID® iDs
between H2 and G4 could be efficiently controlled by addition
Chuan-Feng Chen - https://orcid.org/0000-0002-4347-1406
and removal of acid and base.
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