1,8-Dioxyanthracene-Derived Crown Ethers: Synthesis, Complexation with Paraquat and Assembly of a Tetracationic Cyclophane-Crown Ether Based [2]Catenane

Article abstract of DOI:10.1002/ejoc.201402876

1,8-Dioxyanthracene-based bisarylene crown ethers, composed of ethylene glycol chains and aromatic moieties, have been synthesized. Complexation studies revealed that these crown ethers could form 1:1 complexes with methyl viologen dication (N,N′-dimethyl

Full text of DOI:10.1002/ejoc.201402876

FULL PAPER
DOI: 10.1002/ejoc.201402876
1,8-Dioxyanthracene-Derived Crown Ethers: Synthesis, Complexation with
Paraquat and Assembly of a Tetracationic Cyclophane-Crown Ether Based
[2]Catenane
Bo Tang,[a] Hong-Mei Yang,[a] Wen-Jing Hu,[b] Ming-Liang Ma,*[a] Yahu A. Liu,[c]
Jiu-Sheng Li,*[b] Biao Jiang,*[b] and Ke Wen*[a,b,d]
Keywords: Supramolecular chemistry / Molecular recognition / Crown compounds / Macrocycles / Catenanes
1,8-Dioxyanthracene-based bisarylene crown ethers, com- 9, which is driven predominantly by π-donor/π-acceptor in-
posed of ethylene glycol chains and aromatic moieties, have
been synthesized. Complexation studies revealed that these
crown ethers could form 1:1 complexes with methyl viologen
dication (N,NЈ-dimethyl-4,4Ј-bipyridinium dication; MV2+) in
teractions. The pentaethylene glycol-derived bis-1,8-dioxy-
anthracene-based crown ether 10, however, adopts a cres-
cent-shaped conformation in complex 10ʛMV2+ with the
MV2+ guest being encapsulated by the polyether chains, pro-
a mixed solvent of CDCl3 and CD3CN (1:1 v/v) with associa- pelled mainly by the hydrogen-bonding interactions be-
–1
tion constants in
a
range of (1.2Ϯ0.1)ϫ103
M
to
tween the hydrogen atoms of MV2+ and the oxygen atoms of
the polyether chains of 10. Similarly, the hexaethylene
glycol-derived bis-1,8-dioxyanthracene-based crown ether
11 forms a complex with MV2+. However, only weak π-do-
nor/π-acceptor interactions between the aromatic groups of
the mixed bisarylene crown ethers 12 and 13, and MV2+ were
observed, and construction of tetracationic cyclophane
[CBPQT4+] and crown ether 13 based [2]catenane 15 was
(1.6Ϯ0.2)ϫ104 –1. The structure of the complex and the
M
strength of the π-donor/π-acceptor interactions between the
1,8-dioxyanthracene planes and the pyridinium rings of
MV2+ are highly dependent on the length of the polyether
chains of the ethers. Structural analysis showed that the
tetraethylene glycol-derived bis-1,8-dioxyanthracene-based
crown ether 9 forms a U-shaped host-guest complex with
MV2+ by inserting the coplanar pyridinium rings of MV2+ be- achieved through supramolecular interactions between the
tween the two parallel oriented 1,8-dioxyanthracene units of
[CBPQT4+] ring and naphtho unit in the crown ether.
hosts and secondary ammonium salts[3] or N,NЈ-dialkyl-
4,4Ј-bipyridinium dication guests,[4] has led to the construc-
tion of various mechanically interlocked molecules. A range
of crown ether hosts have since been designed, synthesized,
and used for the creation of interlocked supramolecular
architectures, including pseudorotaxanes, rotaxanes, and
catenanes.[5] There are two approaches that are typically
used to enhance the supramolecular interactions between
the crown ether hosts and the N,NЈ-dialkyl-4,4Ј-bipyridin-
ium dication or pyridinium guests. One is using preorga-
nized structures, such as crown ether based cryptands[6] and
shape-persistent molecular cages,[7,8] and the second is in-
corporating electron-rich aryl moieties, such as naphtho
units, into the crown ether structures to enhance the charge-
transfer interactions between the arylene functions and
N,NЈ-dialkyl-4,4Ј-bipyridinium dications.[9] Anthracene,
which is a highly electron-rich arylene, however, has much
less frequently been incorporated into the structures of
crown ethers,[10] possibly due to its unstable thermo- and
photochemical nature. Indeed, reports on 1,8-dioxy-
anthracene-based crown ethers are almost completely ab-
sent.[11] In this report, the synthesis and characterization of
five 1,8-dioxyanthracene-based bisarylene crown ethers are
described, three of which are composed of two 1,8-dioxy-
Introduction
Since Pedersen’s pioneering work in the synthesis and
group I metal complexation characteristics of crown
ethers,[1] this class of molecules has been developed as the
first generation of macrocyclic hosts and has played a sig-
nificant role in the field of host-guest chemistry.[2] The iden-
tification of host-guest interactions between crown ether
[a] Shanghai Engineering Research Center of Molecular
Therapeutics and New Drug Development, East China Normal
University,
3663 Zhongshan Road, Shanghai 200062, P. R. China
E-mail: mlma@brain.ecnu.edu.cn
kwen@brain.ecnu.edu.cn
[b] Shanghai Advanced Research Institute, Chinese Academy of
Science,
100 Haike Road, Zhangjiang Hi-Tech Park, Pudong, Shanghai,
201210, P. R. China
E-mail: lijs@sari.ac.cn
jiangb@sari.ac.cn
wenk@sari.ac.cn
http://www.sari.ac.cn
[c] Medicinal Chemistry, ChemBridge Research Laboratories Inc.,
San Diego, CA 92127, USA
[d] School of Physical Science and Technology, ShanghaiTech
University,
Shanghai 201210, P. R. China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402876.
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FULL PAPER
Scheme 1. The synthesis of 1,8-dioxyanthracene-based bisarylene crown ethers. Reagents and conditions: (a) 1. CH3COCl/NEt3, 2. Zn/
HAc, 3. NaOH; (b) oligoethylene glycol monotosylate/Cs2CO3, DMF, 90 °C; (c) TsCl/NaOH, THF; (d) 2, (catechol or naphthalene-1,5-
diol)/Cs2CO3, DMF, 90 °C.
anthracene units connected by two tetra-, penta- or hexa- proximately 350 nm,[13] so it is quite reasonable to speculate
ethylene glycol chains. Each of the other two crown ethers that the 1,8-anthracene-based crown ethers would undergo
has one 1,8-dioxyanthracene unit connected through two dimerization. Although 1H NMR spectra indicated that di-
tetraethylene glycol chains to a benzo or a naphtho moiety. merization of the crown ether 9 did not occur in CDCl3
We describe the results of our investigation on host–guest solution, single-crystal structure analysis revealed that bis-
interactions of the synthesized crown ethers with methyl 1,8-dioxyanthracene-based crown ether 9 exists in an intra-
viologen dication (N,NЈ-dimethyl-4,4Ј-bipyridinium dicat- molecular dimerized state, as shown in Figure 1. Given that
ion; MV2+) as well as the formation of the tetracationic topochemical photoreaction of anthracenyl groups could
cyclophane [CBPQT4+]-crown ether based [2]catenane.
take place only when they are positioned at suitable dis-
tances, this result suggests that the intramolecular dimeriza-
tion of 9 probably occurred in the crystalline state.
Results and Discussion
Synthesis of Anthracene-Based Crown Ethers
The 1,8-anthracene-based crown ethers were synthesized
starting with the reduction of 1,8-dihydroxyanthracene-
9,10-dione (1) to anthracene-1,8-diol (2)[12] (Scheme 1). The
latter diol was alkylated by tetra-, penta- or hexaethylene
glycol monotosylate under basic conditions to give diols 3–
5, respectively, which were then reacted with tosyl chloride
to generate the corresponding bistosylates 6–8. The [1+1]
macrocyclization reaction of 6–8 with diol 2 gave the de-
sired anthracene-based crown ethers 9–11, respectively, in
reasonable yields. Similarly, the [1+1] macrocyclization re-
action of 6 with catechol or naphthalene-1,5-diol resulted
in the formation of mixed bisarylene crown ethers 12 and
13, respectively. The structures of the 1,8-anthracene-based
crown ethers 9–13 were confirmed by H, 13C NMR and
MS spectroscopy (see the Supporting Information).
1
Figure 1. Single-crystal structure of intramolecularly dimerized 9;
top: top view of the dimerized anthracene moieties; bottom: side
view of the dimerized anthracene moieties. Hydrogen atoms are
It is known that [4+4] dimerization occurs for anthracene
and its derivatives when irradiated at wavelengths above ap- omitted for clarity.
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1,8-Dioxyanthracene Derived Crown Ethers
Complexation of the 1,8-Dioxyanthracene-Based Crown
Ethers with Methyl Viologen Dications (MV2+
)
The complexation of the 1,8-dioxyanthracene-based
crown ethers with MV2+ was investigated with 1D and 2D
1H NMR spectroscopy, and by mass spectrometry as well
as by single-crystal X-ray diffraction analysis. Mixing a yel-
–
low solution of 9 and a colorless solution of MV2+·2PF6
in CDCl3/CD3CN (1:1 v/v) resulted in a clear dark-red
solution immediately (Figure S1), which was attributed to
the formation of a charge-transfer complex between the
electron-rich anthracene planes of crown ether 9 and the
electron-poor pyridinium rings of MV2+. The complexation
behavior was further examined by using 1H NMR spec-
troscopy in CDCl3 and CD3CN (1:1 v/v). As shown in Fig-
ure 2, upfield shifts for the anthracene H-9 and H-10 signals
(δ = –0.79 and –0.16 ppm) of 9, and α- and β-pyridinium
proton signals (δ = –0.59 and –1.00 ppm) of MV2+, were
Figure 2. 1H NMR (400 MHz, CDCl3/CD3CN, 1:1 v/v): (a) free
MV2+ (1.0 mm); (b) 9 (1.0 mm) + MV2+ (1.0 mm); (c) 9 (1.0 mm).
1
observed in the H NMR spectrum of an equimolar mix-
2.368, 2.559, and 2.559 Å), and the MV2+ guest does not
thread the tetraethylene glycol chains of 9. The complex
9ʛMV2+ is stabilized by π–π stacking, charge transfer, and
by hydrogen-bonding interactions. In the crystal lattice,
one MV2+ molecule was positioned between every two
anthracene planes of different supramolecular complexes
9ʛMV2+, resulting in a stacking array of alternated com-
plex 9ʛMV2+ and MV2+ (see the Supporting Information).
ture of 9 and MV2+, indicating the existence of π-donor/π-
acceptor interactions between the anthracene planes of 9
and the pyridinium rings of MV2+. Upfield shifts for the
proton signals of the tetraethylene glycol chains on 9, and
N-methyl protons of MV2+ (δ = –0.21 ppm) were also ob-
served (Figure 2), which were possibly caused by shielding
effects. 2D 1H NMR NOESY spectrum of the complex
9ʛMV2+ (Figure S2) clearly showed the correlations be-
tween the signals of α- and β-pyridinium protons of MV2+
and the signals of anthracene H-9 and H-10 protons on 9.
The correlations between the signals of N-methyl protons
of MV2+ and those of the tetraethylene glycol protons of 9
were also seen. The results indicated that face-to-face π-
stacking and charge transfer interactions between the an-
thracene planes of 9 and the pyridinium rings of MV2+
could be the main driving force for formation of the com-
plex. Hydrogen-bonding interactions between the N-methyl
groups of MV2+ and the ethylene glycol chains of 9 might
also contribute to stabilizing the complex. A Job plot (Fig-
Figure 3. Single-crystal structure of complex 9ʛMV2+. Hydrogen
–
atoms on host 9 and PF6 counterions are omitted for clarity.
Analogously, the complexation behavior between the
ure S3) based on 1H NMR spectroscopic data demon- penta- and hexaethylene glycol-derived bis-1,8-dioxyanthra-
–
strated that crown ether 9 and MV2+ form a complex in cene-containing crown ethers 10 and 11 with MV2+·2PF6
a 1:1 ratio in CDCl3/CD3CN (1:1 v/v), which was further were studied in CDCl3/CD3CN (1:1 v/v). It was found that
confirmed by ESI-MS spectrometry {m/z 1067.7 assigned the color of the complex 10ʛMV2+ and 11ʛMV2+ solu-
– +
to [9ʛMV2+-PF6 ] ; Figure S4}. The association constant tions was lighter than that of the complex 9ʛMV2+ solu-
(Ka) of the complex 9ʛMV2+ in mixed solvent of CDCl3 tion, with the depth of the red color following a trend of
and CD3CN (1:1 v/v) was determined to be (1.6Ϯ0.2) ϫ 9ʛMV2+ (dark red) Ͼ 10ʛMV2+ (red) Ͼ 11ʛMV2+ (light
104 m–1 with a 1H NMR titration method (see the Support- red) (see the Supporting Information), which could be due
ing Information and Figure S6–S6).
to different strength of charge-transfer interactions between
Single crystals of the complex 9ʛMV2+ were obtained the pyridinium rings of MV2+ and the anthracene planes
1
by slow evaporation of the complex solution in acetonitrile. of the crown ethers. In the H NMR spectra of equimolar
In complex 9ʛMV2+ (Figure 3), the crown ether 9 is folded mixtures of 10 and MV2+, and 11 and MV2+, upfield shifts
in a U-shaped conformation with the two anthracene planes for the anthracene H-9 and H-10 signals on 10 and 11, as
being oriented parallel at a distance of 6.69 Å, and the two well as for the α- and β-pyridinium proton signals of MV2+
coplaner pyridinium rings of the MV2+ guest being interca- (Figures 4 and 5), are smaller than those of the correspond-
lated between the two parallel anthracene planes of 9 in an ing proton signals of the equimolar mixture of 9 and MV2+
.
offset manner, similar to those of anthracene-derived mo- This result suggests a weaker π-donor/π-acceptor interac-
lecular tweezers for complexation of aromatic guests.[14] tion between the anthracene planes of 10 or 11 with the
One α-pyridinium hydrogen atom of MV2+ forms hydrogen pyridinium rings of MV2+, which is consistent with the ligh-
bonds with three oxygen atoms of 9 (C–H···O distances: ter red color of 10ʛMV2+ and 11ʛMV2+ solutions. Upfield
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M.-L. Ma, J.-S. Li, B. Jiang, K. Wen et al.
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v/v). The association constants (Ka) of the complexes
10ʛMV2+ and 11ʛMV2+ in CDCl3/CD3CN (1:1 v/v) were
determined to be (8.9Ϯ0.8) ϫ103 m–1 (Figure S11–S12)
and (6.2Ϯ0.8) ϫ103 m–1 (Figure S115–S16), respectively
(see the Supporting Information).
Figure 4. 1H NMR (400 MHz, CDCl3/CD3CN, 1:1 v/v): (a) free
MV2+ (1.0 mm); (b) 10 (1.0 mm) + MV2+ (1.0 mm); (c) 10 (1.0 mm).
shifts for the N-methyl proton signals of MV2+, as well as
the proton signals of polyether chains, were also observed
in the 1H NMR spectra of the complex solutions of
10ʛMV2+ and 11ʛMV2+, implying these protons are poss-
ibly shielded in the complexes. Furthermore, the 2D 1H
NMR NOESY spectrum (Figure S7) of the complex
10ʛMV2+ solution in CDCl3 and CD3CN (1:1 v/v) revealed
correlations of the α- and β-pyridinium protons of MV2+
with the anthracene and the pentaethylene glycol protons
of 10, and correlations of N-methyl protons of MV2+ with
the pentaethylene glycol protons of 10, which could indicate
the existence of π-donor/π-acceptor interactions between
the anthracene groups on 10 and the pyridinium rings on
MV2+, as well as possible hydrogen-bonding interactions
between the α-, β-pyridinium and N-methyl protons of
MV2+ and the oxygen atoms of the pentaethylene glycol
Figure 5. 1H NMR (400 MHz, CDCl3/CD3CN, 1:1 v/v): (a) free
MV2+ (1.0 mm); (b) 11 (1.0 mm) + MV2+ (1.0 mm); (c) 11 (1.0 mm).
As shown in Figure 6, single crystals of the complex
10ʛMV2+, which were obtained in acetonitrile, reveal a
host-guest complex that is structurally completely different
from that of 9ʛMV2+. In 10ʛMV2+, the host crown ether
10 adopts a crescent-shaped conformation, the guest MV2+
dications are almost completely encapsulated by the poly-
ether chains of the host 10 with its two pyridinium ring
planes being twisted by 30.5°. The host-guest complex
10ʛMV2+ was stabilized by C–H···π and π–π stacking in-
teractions between the pyridinium rings of the MV2+ and
the anthracene planes of 10, and further strengthened by
multiple hydrogen bond (C–H···O distances ranged from
2.221 to 3.220 Å) interactions between the oxygen atoms
1
chains of 10. However, in the 2D H NMR NOESY spec-
trum (Figure S8) of the complex 11ʛMV2+ solution in
CDCl3 and CD3CN (1:1 v/v), only the correlation signals of
α-, β- and N-methyl protons of MV2+ with the hexaethylene
glycol protons of 11 can be observed, implying that the
hydrogen-bonding interactions between the MV2+ protons
and the oxygen atoms of the hexaethylene glycol chains of
11 are the main propelling force for the formation of the
supramolecular complex 11ʛMV2+. Weak π-donor/π-ac-
ceptor interactions between the anthracene groups on 11
and the pyridinium rings of MV2+ are also involved in the
complex 11ʛMV2+, based on the color change observed
upon addition of MV2+ dication to the host solution.
Nonetheless, the supramolecular complex 11ʛMV2+ is pre-
sumed to be formed in a similar way to that of 10ʛMV2+
through the encapsulation of MV2+ guest by hexaethylene
1
glycol chains of 11. Job plots based on H NMR spectro-
scopic data (Figure S9 and Figure S13), and on ESI-MS
spectrometry {m/z 1155.9 and 1243.1, assigned to
– +
– +
[10ʛMV2+-PF6 ] and [11ʛMV2+-PF6 ] , respectively;
Figure 6. Single-crystal structure of complex 10ʛMV2+: (a) top
–
Figure S10 and S14} support structural assignment of 1:1
view; (b) side view. Hydrogen atoms on host 10 and PF6 counter-
complexes 10ʛMV2+ and 11ʛMV2+ in CDCl3/CD3CN (1:1 ions are omitted for clarity.
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1,8-Dioxyanthracene Derived Crown Ethers
of polyether chains on 10 and the hydrogen atoms of the tween the anthracene planes of 13 and the pyridinium ring
pyridinium rings, as well as by the N-methyl protons of planes of MV2+. The correlation signals between the poly-
MV2+. Unfortunately, attempts to grow single crystals of ether protons of 13 and the protons of MV2+ could be due
complex 11ʛMV2+ were unsuccessful.
to hydrogen-bonding interactions between the polyether
The complexation behavior of mixed bisarylene crown oxygen atoms of 13 and the hydrogen atoms of MV2+. A
ether 12 or 13 with MV2+ was also examined in CDCl3/ Job plot based on H NMR spectroscopic data showed the
1
CD3CN (1:1 v/v). Mixing a yellow solution of 12 in CDCl3/ formation of a 1:1 complex 13·MV2+ (Figure S23), which
–
CD3CN (1:1 v/v) and a colorless solution of MV2+·2PF6
was also supported by ESI-MS spectrometry {m/z 1016.9,
– +
in 1:1 molar ratio resulted in immediate color change, im- assigned to [13·MV2+-PF6 ] ; Figure S24}. The association
plying the formation of
a
charge-transfer complex constant (Ka) of the complex 13·MV2+ in CDCl3/CD3CN
12·MV2+. However, no clear color change was observed was determined to be (1.2Ϯ0.1) ϫ103 m–1 (Figure S25–
when the CDCl3/CD3CN (1:1 v/v) solutions of 13 and S26).
MV2+·2PF6– were mixed in a 1:1 molar ratio, suggesting no
charge transfer complex formation between 13 and MV2+
,
possibly due to the unfavorable geometrical arrangement
between the 1,5-dioxynaphthalene and 1,8-dioxyanthracene
planes in 13, which resulted in less effective cooperative in-
1
teraction with a MV2+ guest. In the H NMR spectrum of
–
an equimolar mixture of 12 and MV2+·2PF6 in CDCl3/
CD3CN (1:1 v/v), upfield shifts for the signals of H-9 and
H-10 (δ = –0.20 and –0.04 ppm) of anthracene, the signals
of benzo protons (δ = –0.15 ppm) on 12, and α- and β-
pyridinium proton signals of MV2+ (δ = 0.21 and
0.35 ppm), were observed (Figure 7), implying the existence
of π-donor/π-acceptor interactions between the aryl planes
of the crown ether 12 and the pyridinium rings of MV2+
.
Correlations between the anthracene and benzo proton sig-
nals of 12 and signals of the MV2+ pyridinium protons in
1
the 2D H NMR NOESY spectrum of the mixture 12 and
Figure 7. 1H NMR (400 MHz, CDCl3/CD3CN, 1:1 v/v): (a) free
MV2+·2PF6– in CDCl3/CD3CN (1:1 v/v) also supported the
existence of π-donor/π-acceptor interactions between the
MV2+ (1.0 mm); (b) 12 (1.0 mm) + MV2+ (1.0 mm); (c) 12 (1.0 mm).
aryl planes of 12 and the pyridinium ring planes of MV2+
.
The existence for hydrogen-bonding interactions between
the hydrogen atoms of MV2+ and the oxygen atoms of the
polyether chains of 12 was supported by correlations be-
tween the protons of MV2+ and the protons of polyether
1
chains of 12 (Figure S17). A Job plot based on H NMR
spectroscopic data revealed that host 12 and guest MV2+
form a 1:1 complex 12·MV2+ in CDCl3/CD3CN (Fig-
ure S18), which was supported by ESI-MS spectrometry
– +
{m/z 996.9 assigned to [12·MV2+-PF6 ] ; Figure S19}. The
association constant (Ka) of complex 12·MV2+ in CDCl3/
CD3CN was determined to be (3.1Ϯ0.3) ϫ103 m–1 (Fig-
ure S20–S21). The 1H NMR spectrum of an equimolar mix-
–
ture of 13 and MV2+·2PF6 in CDCl3/CD3CN (1:1 v/v)
showed smaller upfield shifts for the proton signals of H-9
and H-10 (δ = –0.12 and –0.02 ppm) of the anthracene moi-
ety in 13, and α- and β-pyridinium proton signals of MV2+
(δ = –0.11 and –0.19 ppm) (Figure 8), compared with those
in 12; and almost no shifts were observed for the proton
signals of the naphtho moiety in 13, indicating the existence
Figure 8. 1H NMR (400 MHz, CDCl3/CD3CN, 1:1 v/v): (a) free
MV2+ (1.0 mm); (b) 13 (1.0 mm) + MV2+ (1.0 mm); (c) 13 (1.0 mm).
1
As revealed by the 1D and 2D H NMR spectroscopic,
of weak interactions between the anthracene moiety of 13 mass spectrometric, and X-ray crystallographic data, all five
and the pyridinium ring planes of MV2+. In the 2D 1H 1,8-dioxyanthracene-based bisarylene crown ethers were
NMR NOESY spectrum of the mixture of 13 and found to form 1:1 complexes with N,NЈ-dimethyl-4,4Ј-bi-
–
MV2+·2PF6 in CDCl3/CD3CN (Figure S22), weak corre- pyridinium dication (MV2+). In the tetraethylene glycol de-
lation signals between the anthracene protons of 13 and the rived bis-1,8-dioxyanthracene-containing crown ether 9, π-
β-pyridinium protons of MV2+ were observed, hinting at donor/π-acceptor interactions are the dominant noncova-
the existence of weak π-donor/π-acceptor interactions be- lent bond interactions in the formation of the complex
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1
9ʛMV2+ with the MV2+ guest being sandwiched by the two
The H NMR spectrum of 15 in CD3CN confirmed its
anthracene planes of the host. Nevertheless, in the cases of mechanically interlocked structure (Figure 9). The signifi-
bis-1,8-dioxyanthracene-containing crown ethers with cant upfield shift of the H-4/8 protons of the 1,5-dioxy-
longer polyether chains, such as penta- or hexaethylene naphthalene (DNP) unit of the crown ether ring in 15 (rela-
glycol-derived bis-1,8-dioxyanthracene-containing crown tive to the corresponding proton signals of 13) indicates the
ethers 10 or 11, hydrogen-bonding interactions between the CBPQT4+ ring encircles the DNP unit through strong π-
hydrogen atoms of the MV2+ guest and the oxygen atoms donor/π-acceptor interactions. The encircling of the 1,8-di-
of the penta- or hexaethylene glycol chains in 10 or 11 are oxyanthracene unit by the CBPQT4+ ring in [2]catenane 15
the major driving force for the formation of complexes is prohibited due to the size and orientation of the 1,8-di-
10ʛMV2+ or 11ʛMV2+, in which the MV2+ guest is encap- oxyanthracene moiety. Small chemical shifts for the H-9
sulated by the polyether chains of the hosts. For the mixed and H-10 protons of the 1,8-dioxyanthracene moiety of the
bisarylene crown ether 12, the 1,8-dioxyanthracene and crown ether in [2]catenane 15 showed the existence of weak
benzo planes of the host were postulated to interact with supramolecular interactions between the CBPQT4+ ring
the MV2+ guest in a similar way to that of the two 1,8- and the anthracene moiety. ESI-MS analysis also supports
dioxyanthracene planes in 9, but with a weaker binding af- the formation of the CBPQT4+-13 based [2]catenane 15 by
– 3+
finity due to the less electron-rich nature of the benzo plane. the presence of intense peaks at m/z 450.8 ([M-3PF6 ]
)
The smaller association constant of the complex 12·MV2+
,
and 748.7 ([M-2PF6–]2+). The structure of 15, which was
relative to that of 9ʛMV2+, is consistent with such a hy- unambiguously established by single-crystal X-ray diffrac-
pothesis. Although H NMR spectroscopic and mass spec- tion analysis, revealed the formation of a CBPQT4+-13
1
trometric results suggested the formation of a 1:1 complex based [2]catenane (Figure 10), in which the naphtho func-
13·MV2+ upon mixing the 1,8-dioxyanthracene- and 1,5- tion of the crown ether subunit 13 is circulated by the
naphthalene-derived crown ether 13 and MV2+ dications, CBPQT4+ ring through mechanical linkage stabilized by π–
the binding mode is not clear at this stage.
π stacking and hydrogen-bonding interactions, which is
consistent with the results obtained in solution. In the solid
[2]Catenane Assembly
With the 1,8-dioxyanthracene-based crown ethers in
hand, attempts were made to synthesize tetracationic
cyclophane [cyclobis(paraquat-p-phenylene); CBPQT4+
]
aromatic crown ether-based [2]catenanes by utilizing
charged π-donor/π-acceptor template methodology, as
shown in Scheme 2. As the size and geometric parameters
of the 1,8-dioxyanthracene moiety do not allow diparaquat
14 to thread into a tetracationic cyclophane ring, the syn-
thesis of tetracationic cyclophane-crown ether based [2]-
catenanes were unsuccessful in the cases of 9, 10 and 11,
which contain two 1,8-dioxyanthracene functions. However,
in the case of the mixed bisarylene crown ether 13, the π-
electron-deficient aromatic diparaquat 14 could thread
through the π-electron-rich crown ether ring 13 directed by
the π-electron-rich naphtho moiety. Subsequent coupling of
the complex 13·14 with a p-xylylene moiety afforded the
[CBPQT4+]-13 based [2]catenane 15.
1
Figure 9. H NMR spectra (CD3CN, 400 MHz): (top) [2]catenane
15 (1.0 mm); (bottom) 13 (1.0 mm).
Scheme 2.
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1,8-Dioxyanthracene Derived Crown Ethers
state, the crown ether subunit 13 in [2]catenane 15 adopts mation of supramolecular complex 13·MV2+ with a much
a distorted U-shaped conformation, which resulted in the smaller association constant. A tetracationic cyclophane
parallel arrangement of a bipyridinium plane of the [CBPQT4+]-crown ether based [2]catenane was successfully
CBPQT4+ ring and the anthracene moiety, strengthened by constructed through the recognition of naphthalene moiety
π-donor/π-acceptor interactions.
in 13 and the [CBPQT4+] ring, although bis-1,8-dioxyan-
thracene-based crown ethers 9, 10, and 11 could not be used
to construct [2]catenanes due to the size and orientation of
the 1,8-dioxyanthracene planes.
Experimental Section
General Methods: Commercially available chemicals were used
without further purification unless stated otherwise. 1H and 13C
NMR spectra were recorded with 400 MHz spectrometers in
CDCl3 or [D6] DMSO with TMS as the reference. Mass spectra
(ESI analysis) were recorded with Waters ZQ 2000 and Bruker es-
quire 6000 instruments. Single-crystal X-ray diffraction data were
collected with a SMART APEX 2 X-ray diffractometer equipped
with a normal focus M-target X-ray tube. Data reduction included
absorption corrections by the multi-scan method.
Synthesis of 1,8-Dihydroxyanthracene (2): Obtained from 1,8-di-
hydroxyanthracene-9,10-dione (1) by following a reported pro-
cedure. H NMR (400 MHz, [D6]DMSO): δ = 10.32 (s, 2 H), 9.04
(s, 1 H), 8.34 (s, 1 H), 7.47 (d, J = 8.6 Hz, 2 H), 7.34–7.22 (m, 2 H),
6.79 (d, J = 7.1 Hz, 2 H) ppm. 13C NMR (100 MHz, [D6]DMSO): δ
= 153.5, 132.7, 126.2, 124.6, 123.4, 118.3, 115.7, 105.2 ppm. MS
(ESI): m/z calcd. for C14H10O2Na [M + Na]+ 233.06; found 233.31.
Figure 10. Single-crystal structure of [CBPQT4+]-13 based [2]-
1
–
catenane 15. Hydrogen atoms and PF6 counterions are omitted
for clarity.
Synthesis of Tetraethylene Glycol Monotosylate: To a mixture of
tetraethylene glycol (3.88 g, 0.02 mol) in THF (40 mL) was added
sodium hydroxide (2 m, 10 mL). After being stirred at r.t. for
10 min, tosyl chloride (3.8 g, 0.02 mol) in THF (20 mL) was added
dropwise. The reaction mixture was stirred for 3 h, then dilute HCl
was added to adjust the pH to 7. THF was then evaporated under
reduced pressure and the residue was extracted with ethyl acetate
and dried with anhydrous sodium sulfate. After the solvent was
removed in vacuo, the crude product was purified by column
chromatography over silica gel (ethyl acetate/petroleum ether, 1:2)
to afford target compound (4.91 g, 70%). 1H NMR (400 MHz,
CDCl3): δ = 7.79 (d, J = 8.3 Hz, 2 H), 7.36 (d, J = 8.1 Hz, 2 H),
4.19–4.12 (m, 2 H), 3.73–3.56 (m, 14 H), 2.45 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 144.84, 132.9, 129.8, 127.9, 72.5,
70.5, 70.3, 70.8, 69.3, 68.6, 61.5, 21.5 ppm. MS (ESI): m/z calcd.
for C15H24O7SNa [M + Na]+ 371.11; found 371.35.
Conclusions
By employing anthracene-1,8-diol as an aryl component,
we have synthesized five novel 1,8-dioxyanthracene-based
bisarylene crown ethers varied by either the length of poly-
1
ether chains or by the aryl constituents. By means of H
NMR titration, mass spectrometry and X-ray single-crystal
structural analysis, the 1,8-dioxyanthracene-based bisaryl-
ene crown ethers were found to form 1:1 complexes with
N,NЈ-dimethyl-4,4Ј-bipyridinium dication (MV2+
)
in
CDCl3/CD3CN (1:1 v/v) with the association constants
ranged from (1.2Ϯ0.1) ϫ103 m–1 to (1.6Ϯ0.2) ϫ104 m–1.
Results showed that the structures of the resulting supra-
molecular complexes formed between the bis-1,8-dioxy-
anthracene-derived crown ether hosts 9, 10, and 11, and
MV2+ guest are highly dependent on the lengths of the
polyether chains connecting the two 1,8-dioxyanthracene
moieties. For instance, the tetraethylene glycol-derived bis-
1,8-dioxyanthracene-based crown ether 9 was found to
form a sandwiched supramolecular complex 9ʛMV2+
driven predominantly by π-donor/π-acceptor interactions,
whereas crescent-shaped conformations are adopted by the
penta- and hexaethylene glycol-derived bis-1,8-dioxyanthra-
cene-based crown ether hosts 10 and 11 in the supramolec-
ular complexes 10ʛMV2+ and 11ʛMV2+, respectively, with
MV2+ guest encapsulated by the polyether chains of these
crown ether hosts through hydrogen-bonding interactions.
Less stable supramolecular complex 12·MV2+ was formed
due to weaker π-contacts between the benzo plane of the
crown ether 12 and MV2+ dications, whereas the presence
of geometrically mismatched 1,8-dioxyanthracene and 1,5-
Synthesis of Pentaethylene Glycol Monotosylate: Obtained as de-
scribed for tetraethylene glycol monotosylate, yield 67%. 1H NMR
(400 MHz, CDCl3): δ = 7.80 (d, J = 8.2 Hz, 2 H), 7.36 (d, J =
8.1 Hz, 2 H), 4.19–4.12 (m, 2 H), 3.73–3.67 (m, 4 H), 3.65 (d, J =
8.5 Hz, 8 H), 3.60 (d, J = 6.8 Hz, 6 H), 2.45 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 144.9, 132.89, 129.9, 127.99, 70.6,
70.5, 70.4, 70.3, 70.2, 70.1, 69.3, 68.6, 61.5, 21.6 ppm. MS (ESI):
m/z calcd. for C17H28O8SNa [M + Na]+ 415.14; found 415.43.
Synthesis of Hexaethylene Glycol Monotosylate: Obtained as de-
scribed for tetraethylene glycol monotosylate, yield 69%. 1H NMR
(400 MHz, CDCl3): δ = 7.80 (d, J = 7.8 Hz, 2 H), 7.35 (d, J =
7.8 Hz, 2 H), 4.18–4.12 (m, 2 H), 3.76–3.52 (m, 22 H), 2.45 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.8, 132.9, 129.9,
127.9, 72.6, 70.7, 70.6, 70.5, 70.3, 69.4, 68.7, 61.6, 21.6 ppm. MS
(ESI): m/z calcd. for C19H32O9SNa [M + Na]+ 459.17; found
459.41.
Compound 3: A mixture of 1,8-dihydroxyanthracene 2 (0.21 g,
naphthalene moieties in the crown ether 13 led to the for- 1 mmol), tetraethylene glycol monotosylate (0.71 g, 2.1 mmol), and
Eur. J. Org. Chem. 2014, 6925–6934
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6931

M.-L. Ma, J.-S. Li, B. Jiang, K. Wen et al.
FULL PAPER
Cs2CO3 (0.98 g, 3 mmol) in anhydrous DMF (20 mL) was stirred
at 90 °C for 16 h under an argon atmosphere. The reaction mixture
was filtered and then concentrated under reduced pressure. The
crude product was purified by column chromatography over silica
Compound 8: Obtained as described for 6, yield 78%. 1H NMR
(400 MHz, CDCl3): δ = 9.23 (s, 1 H), 8.28 (s, 1 H), 7.76 (d, J =
6.5 Hz, 4 H), 7.54 (d, J = 7.6 Hz, 2 H), 7.33 (s, 2 H), 7.29 (s, 4 H),
6.72 (d, J = 5.8 Hz, 2 H), 4.36 (s, 4 H), 4.11 (s, 4 H), 4.06 (s, 4 H),
gel (ethyl acetate/methanol, 10:1) to afford 3 (0.21 g, 37%). 1H 3.85 (s, 4 H), 3.71 (s, 5 H), 3.65 (s, 5 H), 3.61 (s, 8 H), 3.55 (d, J =
NMR (400 MHz, [D6]DMSO): δ = 9.13 (s, 1 H), 8.45 (s, 1 H), 7.62
(d, J = 8.6 Hz, 2 H), 7.45–7.38 (m, 2 H), 6.91 (d, J = 7.4 Hz, 2 H),
4.57 (s, 2 H), 4.41–4.31 (m, 4 H), 4.00–3.92 (m, 4 H), 3.78–3.71 (m,
7.6 Hz, 8 H), 3.50 (s, 8 H), 2.38 (s, 6 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 154.9, 144.8, 132.9, 129.9, 127.9, 125.7, 125.2, 124.4,
120.4, 115.9, 102.7, 77.7, 77.6, 77.1, 70.9, 70.5, 69.8, 69.3, 68.6,
4 H), 3.63–3.59 (m, 4 H), 3.56–3.52 (m, 4 H), 3.47 (d, J = 19.7 Hz, 67.9, 21.6 ppm. MS (ESI): m/z calcd. for C52H70O18S2Na [M +
12 H) ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 154.2, 132.4, Na]+ 1069.39; found 1069.67.
126.1, 125.1, 123.2, 120.0, 115.0, 103.2, 72.3, 70.3, 69.9, 69.8, 69.7,
Compound 9: A mixture of 2 (52 mg, 0.24 mmol), 6 (0.22 g,
0.24 mmol), and Cs2CO3 (0.4 g, 0.72 mmol) in anhydrous DMF
(20 mL) was stirred at 90 °C for 16 h under an argon atmosphere.
69.0, 67.8, 60.1 ppm. MS (ESI): m/z calcd. for C30H42O10Na [M +
Na]+ 585.27; found 585.51.
The reaction mixture was filtered and then concentrated under re-
duced pressure. The crude product was purified by column
Compound 4: Obtained as described for 3, yield 28%. 1H NMR
(400 MHz, CDCl3): δ = 9.23 (s, 1 H), 8.29 (s, 1 H), 7.55 (d, J =
chromatography over silica gel (ethyl acetate/petroleum ether, 1:1)
8.5 Hz, 2 H), 7.35 (t, J = 8.0 Hz, 2 H), 6.74 (d, J = 7.4 Hz, 2 H),
1
to afford 9 (43 mg, 25%). H NMR (400 MHz, CDCl3): δ = 9.26
4.38 (t, J = 5.0 Hz, 4 H), 4.07 (t, J = 5.0 Hz, 4 H), 3.90–3.84 (m,
(s, 1 H), 8.28 (s, 1 H), 7.54 (d, J = 8.6 Hz, 2 H), 7.35–7.28 (m, 2
4 H), 3.74–3.70 (m, 4 H), 3.68 (dd, J = 9.3, 4.9 Hz, 8 H), 3.63–3.58
H), 6.64 (d, J = 7.4 Hz, 2 H), 4.34–4.29 (m, 4 H), 4.10–4.06 (m, 4
(m, 12 H), 3.56–3.52 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 154.9, 132.9, 125.6, 125.2, 124.4, 120.4, 115.9, 102.7, 77.4, 77.1,
H), 3.94–3.89 (m, 4 H), 3.82–3.76 (m, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 155.0, 132.9, 125.6, 125.1, 124.4, 123.8,
76.8, 72.6, 71.1, 70.6, 70.2, 69.8, 67.9, 61.6 ppm. MS (ESI): m/z
116.0, 102.5, 71.2, 70.8, 69.9, 68.2 ppm. MS (ESI): m/z calcd. for
calcd. for C34H50O12Na [M + Na]+ 673.32; found 673.51.
C44H48O10Na [M + Na]+ 759.31; found 759.65.
1
Compound 5: Obtained in as described for 3, yield 35%. H NMR
1
Compound 10: Obtained as described for 9, yield 23%. H NMR
(400 MHz, [D7]DMF): δ = 9.32 (s, 1 H), 8.51 (s, 1 H), 7.68 (d, J =
(400 MHz, CDCl3): δ = 9.24 (s, 1 H), 8.28 (s, 1 H), 7.55 (d, J =
8.5 Hz, 2 H), 7.46 (t, J = 8.0 Hz, 2 H), 6.98 (d, J = 7.4 Hz, 2 H),
4.48–4.41 (m, 4 H), 4.12–4.06 (m, 4 H), 3.89–3.83 (m, 4 H), 3.73–
8.5 Hz, 2 H), 7.33 (t, J = 8.0 Hz, 2 H), 6.68 (d, J = 7.4 Hz, 2 H),
4.34 (t, J = 4.8 Hz, 4 H), 4.06 (t, J = 4.8 Hz, 4 H), 3.93–3.84 (m,
3.70 (m, 4 H), 3.64–3.56 (m, 28 H), 3.51 (d, J = 5.2 Hz, 4 H) ppm.
4 H), 3.77–3.66 (m, 8 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
13C NMR (100 MHz, [D7]DMF): δ = 155.1, 133.2, 126.3, 125.5,
154.9, 132.9, 125.6, 125.1, 124.4, 120.4, 115.9, 102.5, 71.5, 70.7,
124.5, 120.4, 115.7, 103.3, 73.0, 71.1, 70.6, 69.8, 68.5, 61.2 ppm.
69.8, 68.1 ppm. MS (ESI): m/z calcd. for C48H56O12Na [M + Na]+
MS (ESI): m/z calcd. for C38H58O14Na [M + Na]+ 761.37; found
847.37; found 847.52.
761.66.
1
Compound 11: Obtained as described for 9, yield 18%. H NMR
(400 MHz, CDCl3): δ = 9.23 (s, 1 H), 8.27 (s, 1 H), 7.53 (d, J =
8.5 Hz, 2 H), 7.32 (t, J = 7.9 Hz, 2 H), 6.68 (d, J = 7.3 Hz, 2 H),
4.33 (t, J = 4.2 Hz, 4 H), 4.04 (t, J = 4.2 Hz, 4 H), 3.89–3.83 (m,
4 H), 3.73–3.68 (m, 4 H), 3.63 (d, J = 6.2 Hz, 8 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 155.0, 132.9, 125.6, 125.2, 124.4, 120.4,
116.0, 102.6, 70.8, 70.7, 70.6, 68.8, 68.0 ppm. MS (ESI): m/z calcd.
for C52H64O14Na [M + Na]+ 935.42; found 935.77.
Compound 6: To a solution of 3 (0.2 g, 0.36 mmol) in THF (15 mL)
was added sodium hydroxide (2 m, 1 mL). After being stirred at r.t.
for 10 min, tosyl chloride (0.15 g, 0.8 mmol) in THF (5 mL) was
added dropwise. The reaction mixture was then stirred for 3 h. Di-
lute HCl was added to adjust the pH to 7. THF was then evapo-
rated under reduced pressure and the residue was extracted with
ethyl acetate and dried with anhydrous sodium sulfate. After the
solvent was removed in vacuo, the crude product was purified by
column chromatography over silica gel (ethyl acetate/petroleum
Compound 12: A mixture of catechol (28 mg, 0.25 mmol), 6 (0.22 g,
0.25 mmol), and Cs2CO3 (0.25 g, 0.75 mmol) in anhydrous DMF
(20 mL) was stirred at 90 °C for 16 h under an argon atmosphere.
The reaction mixture was filtered and then concentrated under re-
duced pressure. The crude product was purified by column
chromatography over silica gel (ethyl acetate/methanol, 50:1) to af-
1
ether, 2:1) to afford 6 (0.26 g, 86%). H NMR (400 MHz, CDCl3):
δ = 9.23 (s, 1 H), 8.28 (s, 1 H), 7.73 (d, J = 8.3 Hz, 4 H), 7.54 (d,
J = 8.5 Hz, 2 H), 7.37–7.31 (m, 2 H), 7.26 (d, J = 8.1 Hz, 4 H),
6.72 (d, J = 7.4 Hz, 2 H), 4.36 (t, J = 5.0 Hz, 4 H), 4.09–4.02 (m,
8 H), 3.83 (dd, J = 5.6, 3.8 Hz, 4 H), 3.69–3.64 (m, 4 H), 3.59 (dd,
J = 9.5, 5.0 Hz, 8 H), 3.54–3.48 (m, 4 H), 2.36 (s, 6 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 154.9, 144.8, 132.9, 129.8, 127.9,
125.6, 125.1, 124.4, 120.4, 115.9, 102.7, 71.0, 70.7, 70.6, 70.5, 69.7,
69.2, 68.6, 67.9, 21.5 ppm. MS (ESI): m/z calcd. for
C44H54O14S2Na [M + Na]+ 893.29; found 893.51.
1
ford 12 (40 mg, 25%). H NMR (400 MHz, CDCl3): δ = 9.26 (s, 1
H), 8.29 (s, 1 H), 7.55 (d, J = 8.5 Hz, 2 H), 7.33 (t, J = 7.9 Hz, 2
H), 6.92–6.81 (m, 4 H), 6.68 (d, J = 7.4 Hz, 2 H), 4.38–4.31 (m, 4
H), 4.14–4.10 (m, 4 H), 4.10–4.05 (m, 4 H), 3.94–3.89 (m, 4 H),
3.89–3.84 (m, 4 H), 3.80–3.74 (m, 8 H), 3.72 (d, J = 5.2 Hz, 4
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 155.0, 148.9, 132.9,
125.6, 125.1, 124.4, 121.5, 120.4, 116.0, 114.3, 102.4, 71.1, 70.8,
69.8, 69.0, 68.1 ppm. MS (ESI): m/z calcd. for C36H44O10Na [M +
Na]+ 659.28; found 659.57.
Compound 7: Obtained as described for 6, yield 76%. 1H NMR
(400 MHz, CDCl3): δ = 9.23 (s, 1 H), 8.30 (s, 1 H), 7.77 (d, J =
8.1 Hz, 4 H), 7.56 (d, J = 8.5 Hz, 2 H), 7.35 (t, J = 8.0 Hz, 2 H),
7.30 (d, J = 8.0 Hz, 4 H), 6.74 (d, J = 7.4 Hz, 2 H), 4.38 (t, J =
Compound 13: A mixture of 1,5-dihydroxynaphthalene (64 mg,
5.0 Hz, 4 H), 4.12–4.09 (m, 4 H), 4.07 (t, J = 5.0 Hz, 4 H), 3.88– 0.4 mmol), 6 (0.23 g, 0.4 mmol) and Cs2CO3 (0.39 g, 1.2 mmol) in
3.84 (m, 4 H), 3.73–3.69 (m, 4 H), 3.65–3.57 (m, 12 H), 3.51 (m, 8 anhydrous DMF (20 mL) was stirred at 90 °C for 16 h under an
H), 2.41 (s, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 154.9, argon atmosphere. The reaction mixture was filtered and then con-
144.9, 132.9, 129.8, 127.9, 125.6, 125.2, 124.4, 120.4, 115.9, 102.6,
71.1, 70.7, 70.6, 70.5, 70.4, 69.7, 69.2, 68.6, 67.8, 21.6 ppm. MS
(ESI): m/z calcd. for C48H62O16S2Na [M + Na]+ 981.34; found
981.61.
centrated under reduced pressure. The crude product was purified
by column chromatography over silica gel (ethyl acetate/petroleum
ether, 1:1) to afford 13 (52 mg, 19%). 1H NMR (400 MHz, CDCl3):
δ = 9.18 (s, 1 H), 8.29 (s, 1 H), 7.89 (d, J = 8.4 Hz, 2 H), 7.55 (d,
6932
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2014, 6925–6934

1,8-Dioxyanthracene Derived Crown Ethers
J = 8.5 Hz, 2 H), 7.37–7.29 (m, 4 H), 6.83 (d, J = 7.6 Hz, 2 H), fined isotropically. Experimental data for 9, 9ʛMV2+, 10ʛMV2+
6.70 (d, J = 7.4 Hz, 2 H), 4.29 (t, J = 4.6 Hz, 8 H), 3.90 (dd, J = and [CBPQT4+]-13 are shown below.
10.9, 5.5 Hz, 8 H), 3.75–3.70 (m, 4 H), 3.64–3.60 (m, 4 H), 3.56
Single-Crystal Structure of 9: C48H56Cl3O10; Mr = 899.27; T =
173(2) K; triclinic; space group P1; a = 11.761(2), b = 13.549(3), c
(m, 8 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 155.0, 154.4,
¯
132.9, 127.0, 125.6, 125.0, 124.5, 120.4, 116.0, 114.7, 106.7, 102.8,
71.2, 71.0, 70.7, 70.6, 69.9, 69.5, 69.3, 67.6 ppm. MS (ESI): m/z
calcd. for C40H46O10Na [M + Na]+ 709.30; found 709.61.
= 15.333(3) Å, α =68.817(3)°, β = 82.684(3)°, γ = 81.438(3)°; V =
2245.7(7) Å3;
Z = 2; ρcalcd. = =
1.330 g/cm3; crystal size
0.090ϫ0.060ϫ0.040 mm; μ = 0.262 mm–1; reflections collected
Aromatic Diparaquat 14: A solution of 4,4Ј-bipyridine (0.31 g,
13667; unique reflections 7810; data/restraints/parameters 7810/18/
2 mmol), p-xylylene dibromide (0.26 g, 1 mmol) in anhydrous 555; GOF on F2 1.016; Rint for independent data 0.0400; final R1
MeCN (10 mL) was stirred in a sealed tube at 60 °C for 8 h. After
the solvent was removed in vacuo, the crude product was purified
by column chromatography over silica gel (methanol/2 m NH4Cl/
MeNO2, 10:7:1) to obtain a yellow solid. Then the solid was dis-
solved in hot water, and a saturated aqueous solution of NH4PF6
was added until no further precipitation was observed. The precipi-
tate was filtered and dried to afford 14 (0.33 g, 45%). 1H NMR
(400 MHz, [D6]DMSO): δ = 9.34 (d, J = 6.9 Hz, 4 H), 8.87 (d, J
= 6.1 Hz, 4 H), 8.64 (d, J = 6.8 Hz, 4 H), 8.01 (d, J = 6.2 Hz, 4
H), 7.66 (s, 4 H), 5.88 (s, 4 H) ppm.
= 0.0759, wR2 = 0.2168; R indices (all data) R1 = 0.11498, wR2 =
0.3001; largest diff. peak and hole: 0.816 and –0.776 eÅ–3.
Single-Crystal Structure of 9ʛMV2+: C76H88F24N8O10P4; Mr
=
1853.42; T = 173(2) K; orthorhombic; space group pbam; a =
20.5094(5), b = 31.6190(8), c = 13.5291(4) Å, α = β = γ = 90°; V =
8773.4(4) Å3;
Z = 4; ρcalcd. = =
1.403 g/cm3; crystal size
0.600ϫ0.070ϫ0.060 mm; μ = 1.768 mm–1; reflections collected
43207; unique reflections 7991; data/restraints/parameters 7991/88/
690; GOF on F2 1.386; Rint for independent data 0.0799; final R1
= 0.1033, wR2 = 0.3102; R indices (all data) R1 = 0.1129, wR2 =
0.3263; largest diff. peak and hole: 0.899 and –0.714 eÅ–3.
[2]Catenane 15: A mixture of 13 (68 mg, 0.1 mmol), 14 (36 mg,
0.05 mmol), and p-xylylene dibromide (13 mg, 0.05 mmol) in anhy-
drous DMF (5 mL) was stirred under 15 kbar of nitrogen for 8 d,
the color of the solution gradually became purple. After the solvent
was removed in vacuo, the crude product was purified by column
chromatography over silica gel (methanol/2 m NH4Cl/MeNO2,
4:4:2) to obtain a purple solid. The solid was dissolved in hot water,
and a saturated aqueous solution of NH4PF6 was added until no
further precipitation was observed. The precipitate was filtered and
Single-Crystal Structure of 10ʛMV2+
:
C60H70F12N2O12P2;
¯
Mr = 1301.12; T = 173(2) K; trigonal; space group R3:h; a =
b = 23.096(4), c = 59.589(9) Å, α = β = 90°, γ = 120°; V =
27527(9) Å3;
Z = 18; ρcalcd. = =
1.413 g/cm3; crystal size
0.490ϫ0.400ϫ0.360 mm; μ = 0.170 mm–1; reflections collected
33242; unique reflections 13849; data/restraints/parameters 13849/
27/820; GOF on F2 1.226; Rint for independent data 0.0389; final
R1 = 0.1089, wR2 = 0.3105; R indices (all data) R1 = 0.1573, wR2
= 0.3535; largest diff. peak and hole: 2.465 and –1.189 eÅ–3.
1
dried to afford 15 (17 mg, 19%). H NMR (400 MHz, CD3CN): δ
= 8.78 (d, J = 6.5 Hz, 4 H), 8.45 (d, J = 6.0 Hz, 4 H), 8.30 (s, 1
H), 8.23 (s, 1 H), 7.98 (d, J = 0.5 Hz, 4 H), 7.85 (d, J = 0.9 Hz, 4
H), 7.52 (d, J = 8.7 Hz, 2 H), 7.39 (t, J = 7.9 Hz, 2 H), 7.10 (d, J
= 6.0 Hz, 4 H), 6.97 (d, J = 5.4 Hz, 4 H), 6.84 (d, J = 7.4 Hz, 2
H), 4.22 (d, J = 3.1 Hz, 4 H), 4.19–4.15 (m, 4 H), 4.15–4.11 (m, 4
H), 3.97–3.91 (m, 4 H), 3.85–3.80 (m, 4 H), 3.79–3.74 (m, 4 H),
3.71–3.66 (m, 4 H), 3.66–3.58 (m, 4 H), 2.25 (d, J = 8.2 Hz, 2
H) ppm. 13C NMR (125 MHz, CD3CN): δ = 155.1, 151.8, 145.4,
144.9, 144.5, 137.1, 133.1, 131.9, 131.74, 128.37, 126.86, 126.19,
126.11, 124.85, 124.79, 124.42, 121.0, 115.5, 108.8, 105.6, 104.8,
71.4, 70.7, 70.5, 70.2, 69.5, 69.3, 68.6, 68.3, 65.5 ppm. MS (ESI):
m/z calcd. for C76H78F12N4O10P2 [M + 2PF6]2+ 748.25; found
748.72; m/z calcd. for C76H78F6N4O10P [M + 3PF6]3+ 450.51; found
450.82.
Single-Crystal Structure of [2]Catenane 15: C86H93F24N9O10P4; Mr
= 1992.57; T = 173(2) K; monoclinic; space group Cc; a =
24.512(3); b = 14.1398(15); c = 27.513(3) Å, α = γ = 90°, β =
107.249(3)°; V = 9107.0(18) Å3; Z = 4; ρcalcd. = 1.453 g/cm3; crystal
size = 0.540ϫ0.380ϫ0.350 mm; μ = 0.194 mm–1; reflections col-
lected 31370; unique reflections 16643; data/restraints/parameters
16643/16/1202; GOF on F2 1.071; Rint for independent data 0.0353;
final R1 = 0.0594, wR2 = 0.1653; R indices (all data) R1 = 0.0737,
wR2 = 0.1954; largest diff. peak and hole: 1.013 and –0.420 eÅ–3.
Supporting Information (see footnote on the first page of this arti-
cle): Synthesis and NMR spectra of 2–15 and complexes, details of
association constant determination, Job plots and MS spectra. So-
lid-state packing of complex 9ʛMV2+
.
N,NЈ-Dimethyl-4,4Ј-bipyridinium Dications (MV2+·2PF6): A solu-
tion of 4,4Ј-bipyridine (0.16 g, 1 mmol) and iodomethane (155 μL,
2.5 mmol) in anhydrous MeCN (10 mL) was stirred in a sealed tube
at 60 °C for 8 h. After the solution was cooled to room tempera-
ture, the yellow precipitate was filtered and washed with MeCN.
The solid was then dissolved in hot water and a saturated aqueous
solution of NH4PF6 was added until no further precipitation was
observed. The precipitate was filtered and dried to afford
MV2+·2PF6 (0.26 g, 53%). 1H NMR (400 MHz, CD3CN/CDCl3,
1:1 ): δ = 8.87 (d, J = 6.2 Hz, 4 H), 8.40 (d, J = 5.7 Hz, 4 H), 4.43
(s, 6 H) ppm.
Acknowledgments
This work was supported by the National Natural Science Founda-
tion of China (NSFC) (grant numbers 21371177, 21071053,
21002031), the Shanghai Commission for Science and Technology
(12DZ1100901) and by the Chinese Academy of Sciences (Strategic
Priority Research Program, grant number XDA01020304). The au-
thors would also like to thank Dr. Alex Cortez (Genomics Institute
of the Novartis Research Foundation, San Diego, CA 92121, USA)
for his critical reading of the manuscript.
Crystal Structure Data Collection and Refinement: Intensity data
were collected at 173(2) K with a Bruker SMART APEX 2 X-ray
diffractometer equipped with a normal focus Mo-target X-ray tube
(λ = 0.71073 Å). Data reduction included absorption corrections
by the multiscan method. The structures were solved by direct
methods and refined by full-matrix least-squares using SHELXS-
97. All non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were included at their geometrically ideal positions and re-
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