Three-dimensional supramolecular polymers driven by rigid tetrahedral building blocks through tetrathiafulvalene radical cation dimerization

Article abstract of DOI:10.1016/j.tet.2014.05.035

Rigid tetrahedral compounds T1 and T2 that bear four tetrathiafulvalene (TTF) units, which are connected to a tetraphenylmethane core by the ethynylene or amide linker were designed and prepared. Upon one-electron oxidation of the TTF units by Fe(ClO₄)₃, the resulting TTF⁺ radical cations stacked intermolecularly to give rise to three-dimensional supramolecular polymers, which were supported by UV-vis spectroscopy, cyclic voltammetry, dynamic light scattering, and scanning electron microscopy.

Full text of DOI:10.1016/j.tet.2014.05.035

Tetrahedron 70 (2014) 4778e4783
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Three-dimensional supramolecular polymers driven by rigid
tetrahedral building blocks through tetrathiafulvalene radical cation
dimerization
*
*
Lan Chen, Shao-Chen Zhang, Hui Wang, Ya-Ming Zhou , Zhan-Ting Li, Dan-Wei Zhang
Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 April 2014
Received in revised form 2 May 2014
Accepted 8 May 2014
Available online 21 May 2014
Rigid tetrahedral compounds T1 and T2 that bear four tetrathiafulvalene (TTF) units, which are con-
nected to a tetraphenylmethane core by the ethynylene or amide linker were designed and prepared.
Upon one-electron oxidation of the TTF units by Fe(ClO4)3, the resulting TTFꢀþ radical cations stacked
intermolecularly to give rise to three-dimensional supramolecular polymers, which were supported by
UVevis spectroscopy, cyclic voltammetry, dynamic light scattering, and scanning electron microscopy.
Ó 2014 Elsevier Ltd. All rights reserved.
Keywords:
Supramolecular polymer
Tetrathiafulvalene
Hydrophobic effect
Aromatic stacking
Cooperativity
1. Introduction
decade, several supramolecular methods have been developed to
enhance the stability of this dimeric motif.8e10
In recent years, there has been considerable interest in de-
veloping supramolecular polymers by holding monomers with
discrete non-covalent forces, such as intermolecular hydrogen
bondings, hosteguest molecular recognitions, and so on.1,2 Most of
the reported supramolecular polymers are constructed from simple
ditopic monomers, which lead to the formation of linear backbones.
Many examples of cross-linked supramolecular polymers have also
been reported, among which are respectable cases with the func-
tions of self-healing, stimuli responsiveness, etc.3 Given the ex-
tensive investigations on the constructions and functions of three-
dimensional (3D) metal-organic and covalent-organic frame-
works,4 it would be of importance to develop 3D soft networks
through self-assembly strategy. Tetraphenyl-methane has been
demonstrated as a useful subunit for the design of preorganized
tetratopic building blocks for the generation of macromolecular
systems.5 As a versatile electron donor, tetrathiafulvalene (TTF) has
been widely applied in researches in materials and supramolecular
sciences.6 Wudl and Torrance reported that, upon one-electron
oxidation, the resulting TTFꢀþ radical cation can dimerize in solid
state.7 However, the stability of the dimer is very low. In the past
We recently reported that tetraphenylmethane-based tetratopic
building blocks that connect four TTF units with flexible linkers
could self-assemble into stable 3D supramolecular polymers after
the TTF units were oxidized to TTFꢀþ 11
To exploit the factors that
.
affect the formation of this kind of supramolecular polymers, we
have synthesized two new tetrahedral building blocks T1 and T2,
whose four TTF units are connected to the central tetraphenyl-
methane unit with rigid ethynylene or amide linkers (Fig. 1). We
herein describe their self-assembly into 3D supramolecular poly-
mers driven by the dimerization of the TTFꢀþ units.
2. Results and discussion
2.1. Synthesis
Synthetic routes for compounds T1, T2, M1, and M2 are shown in
Scheme 1. Compound 1 was first synthesized according to reported
literature.12a Treatment of 1 with bromine afforded compound 2 in
80% yield. The tetrabromide was then reacted with trimethylsily-
lacetylene, which was followed by removal of the trimethylsilyl
group with sodium hydroxide, to give tetraalkyne 3 in 40% yield.12b
Compound 1 was further nitrated to give 4, which was then treated
with stannous chloride to produce 5.12a Compounds 7 and 8 were
* Corresponding authors. Tel.: þ86 21 65643576; fax: þ86 21 65641740; e-mail
address: zhangdw@fudan.edu.cn (D.-W. Zhang).
prepared from commercially available tetrathiafulvalene
6
0040-4020/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2014.05.035

L. Chen et al. / Tetrahedron 70 (2014) 4778e4783
4779
Fig. 1. Rigid tetrahedral compounds T1 and T2 bearing four TTF units and model
compounds M1 and M2.
according to reported methods.13a Then Sonogashira cross-
coupling reaction of 7 with 3 or ethynylbenzene afforded T1 in
20% yield and M113b in 50% yield, respectively. Hydrolysis of com-
pound 8 in aqueous sodium hydroxide solution produced the cor-
responding acid, which was further reacted with 5 or aniline to
afford T2 in 48% yield and M213c in 58% yield, respectively.
2.2. UVevis spectroscopy
The self-assembly of compounds T1, M1, T2, and M2 at different
oxidation states for the TTF units, which was realized by adding
different equiv of Fe(ClO4)3, were first studied by UVevis spec-
troscopy. For T1 and M1, the experiments were conducted in chlo-
roform, and for T2 and M2, the chloroform/acetonitrile mixture (2:1
v/v) was used.14 Adding 0.25, 0.5, 0.75, and 1 equiv of Fe(ClO4)3,
which were relative to the concentration of the TTF unit, to the
solution of T1 (0.05 mM) in chloroform caused the TTF unit to be
oxidized to its radical cation TTFꢀþ gradually.14 In the recorded ab-
sorption spectra (Fig. 2), in addition to the absorption bands cen-
tered at 410 and 600 nm, which could be assigned to the TTFꢀþ
monomer,14 two absorption bands, centered around 845 and
1600 nm, were also displayed. These two bands are typical for the
radical cation dimer (TTFꢀþ
)
2
and the mixed-valence dimer
(TTF)ꢀ2þ 8,15 respectively. The intensity of the absorption peak around
,
1600 nm reached maximum when 2 equiv of Fe(ClO4)3 relative toT1
was added (Fig. 2b,c), which allowed for the oxidation of half of the
TTF units to the TTFꢀþ unit. With the addition of more Fe(ClO4)3, the
absorption band became weakened because more neutral TTF units
were oxidized to TTFꢀþ and when 4 equiv of Fe(ClO4)3 relative to T1
was added, the absorption band around 845 nm became the
strongest as all the TTF units were oxidized to TTFꢀþ and thus the
concentration of (TTFꢀþ
) reached to its maximum (Fig. 2a). For
2
control compound M1, with the addition of Fe(ClO4)3, only the ab-
sorption of the radical cationTTFꢀþ was observed (Fig. 2d), indicating
that its dimerization tendency was very weak.
Scheme 1. The synthesis of compounds T1, T2, M1, and M2.
In chloroform, when the TTF units of compound T2 (0.025 mM)
were oxidized to radical cation TTFꢀþ, green precipitation was
formed due to the strong dimerization of TTFꢀþ. In the chloroform/
acetonitrile (2:1) mixture containing 1% 2-phenoxyethanol, no
precipitation occurred. Thus, the UVevis spectra were recorded in
this solvent system. The spectra, together with those of M2, are
provided in Fig. 3. Again, the spectra of T2 displayed the absorption
bands of radical cation dimer (TTFꢀþ)2, which was centered around
800 nm (Fig. 3a), and mixed-valence dimer (TTF)ꢀ2þ, which was
centered around 1450 nm (Fig. 3b,c). In contrast, compound M2 did
not exhibit similar absorption bands (Fig. 3d). On the basis of
UVevis dilution experiments, we could determine the apparent
association constants (Ka) of the dimer of the TTFꢀþ unit of T1 in
chloroform and T2 in chloroform and acetonitrile (2:1) were
2.2ꢁ104 and 5.9ꢁ104 Mꢂ1, respectively, by fitting the absorption of
(TTFꢀþ 2 to the 1:1 nonlinear equation.10b,11
)
Given the rigidity of tetrahedral backbone of compounds T1 and
T2, it was not possible for their peripheral TTFꢀþ units to undergo
intramolecular dimerization. Thus, their stacking should occur

4780
L. Chen et al. / Tetrahedron 70 (2014) 4778e4783
Fig. 2. UVevis absorption spectra of (aec) T1 and (d) M1, after different equiv of
Fe(ClO4)3 was added, in chloroform at 25 ꢃC ([TTF]¼0.2 mM, 1.0 cm path length).
intermolecularly. The fact that no absorption of (TTFꢀþ
was observed for M1 and M2 suggested that the preorganized tet-
rahedral backbone of T1 and T2 provided cooperativity for the
homodimerization of the TTFꢀþ unit and its stacking with the neutral
)
2
or (TTF)ꢀ2þ
Fig. 3. UVevis absorption spectra of (aec) T2 and (d) M2, when different equiv of
Fe(ClO4)3 was added, in chloroform and acetonitrile (2:1, v/v) at 25 ꢃC ([TTF]¼0.1 mM,
1.0 cm path length).

L. Chen et al. / Tetrahedron 70 (2014) 4778e4783
4781
TTF unit through the formation of 3D supramolecular polymers,10b,11
as shown in Fig. 4. For both T1 and T2 (0.05 mM), when the UVevis
spectra were recorded in more polar chloroform and acetonitrile
mixture (1:1, v/v), neither the absorption of the (TTFꢀþ)2 dimer nor
that of the (TTF)ꢀ2þ mixed-valence dimer was observed. This obser-
vation indicates that the increase of the polarity of the medium
weakened the stacking of the TTFꢀþ via better solvation probably.
oxidation and reduction peaks of compounds T1 and T2 appeared
with a lower potential. This observation indicated that, for both
compounds, the two oxidation processes, that is, TTF/TTFꢀþ and
TTFꢀþ/TTF2þ, were easier to occur, whereas the two reduction
processes, that is, TTF2þ/TTFꢀþ and TTFꢀþ/TTF, were more diffi-
cult to occur. The shifting of the first oxidation and the second re-
duction to the low-potential direction may be attributed to the
formation of (TTFꢀþ
)
2
by TTFꢀþ, which caused TTF to lose the first
electron more easily and led to the formation of the 3D supramo-
lecular networks. The fact that the second oxidation appeared with
a lower potential implied that the TTFꢀþ units in the dimeric state
lost another electron more easily. It is intriguing that the first re-
duction also shifted to the low-potential direction. One possible
reason for this result is that their large tetrahedral backbone made
the octacationic species to diffuse much more slowly, which
delayed the reduction of TTF2þ to TTFꢀþ
.
2.4. Dynamic light scattering (DLS)
It was envisioned that the 3D supramolecular networks formed
by T1 and T2 in the TTFꢀþ state would produced aggregates of large
size. We thus performed DLS experiments for T1 in chloroform and
T2 in chloroform and acetonitrile (2:1) after the TTF units were
oxidized to TTFꢀþ. The apparent hydrodynamic diameter (DH) of the
formed aggregates was determined to be 116.5 and 84.1 nm (Fig. 6),
respectively. Under the identical measurement conditions, both the
solution of M1 and M2 did not produce any large aggregates of
>3 nm in size. Thus, the above large DH values could be regarded as
strong evidence for the formation of 3D supramolecular networks
for T1 and T2 through the intermolecular dimerization of their
appended TTFꢀþ units.
Fig. 4. Schematic representation of the 3D supramolecular polymers formed by tet-
rahedral compounds T1 and T2 via intermolecular dimerization of their TTFꢀþ units.
2.3. Cyclic voltammetry (CV)
CV experiments were also carried out to investigate the elec-
trochemical properties of T1 and T2 and the voltammograms, to-
gether with those of M1 and M2, are shown in Fig. 5. All the
potentials were referenced against an Ag/AgCl electrode. All the
four compounds gave rise to two oxidation and reduction peaks.
However, compared with that of the controls M1 and M2, both the
25
84.1 nm
20
116.5 nm
15
10
5
(a)
0.98
1.0
0.61
0.54
0
0.48
10
100
DH (nm)
1000
0.91
T1
M1
ꢀ
ꢀ
0.77
Fig. 6. DLS results of T14( þ) (e,e) in CHCl3 ([TTF]¼0.2 mM), and T24( þ) (eBe) in
0.38
0.50
CHCl3/MeCN 2:1 ([TTF]¼0.08 mM) at 25 ꢃC.
0.00
0.25
0.75
1.00
1.25
2.5. Scanning electron microscopy (SEM)
E/V
(b)
0.97
In order to investigate the morphological character of the su-
pramolecular aggregates formed by T1 and T2, SEM images were
also recorded after evaporating their respective solution (Fig. 7).
T2
M2
0.53
0.90
0.48
0.37
0.82
0.90
0.46
0.00
0.25
0.50
0.75
1.00
1.25
E/V
Fig. 5. Cyclic voltammograms of (a) T1 and M1 in chloroform ([TTF]¼0.2 mM), and (b)
T2 and M2 in chloroform and acetonitrile (2:1) ([TTF]¼0.1 mM) at 25 ꢃC. Electrolyte:
Bu4NPF6 (0.1 M), the scan rate: 100 mV/s.
Fig. 7. SEM images of the samples of (a) T1 (0.1 mM) in chloroform, and (b) T2
(0.1 mM) in chloroform and acetonitrile (2:1) on mica after their TTF units were oxi-
dized to TTFꢀþ and the solvent was evaporated.

4782
L. Chen et al. / Tetrahedron 70 (2014) 4778e4783
The SEM images of both samples showed the formation of
spherical particles with the size ranging from 1 m to 10 m.
4.3. Characterization of compounds M1 and M2
m
m
Again, similar spherical particles were not observed from the im-
ages of M1 or M2. Thus, the large spherical particles observed for
the samples of T1 and T2 should reflect that they formed 3D su-
pramolecular networks in solution after their TTF units were oxi-
Compound M1:13b 1H NMR (400 MHz, CDCl3)
d 7.45e7.44
(m, 2H), 7.35e7.33 (m, 3H), 6.55 (s, 1H), 6.33 (s, 2H). Compound
M2:13c 1H NMR (400 MHz, DMSO-d6)
d
10.23 (s, 1H), 7.80 (s, 1H),
7.60 (d, J¼8.2 Hz, 2H), 7.34 (t, J¼7.9 Hz, 2H), 7.12e7.09 (m, 1H), 6.76
dized to TTFꢀþ
.
(s, 2H).
3. Conclusion
Acknowledgements
We have demonstrated that rigid tetrahedral TTF molecules
could self-assemble into 3D supramolecular networks in solution
after their peripheral TTF units were oxidized to radical cations,
which is driven by preorganization-promoted dimerization of the
radical cations. This work, together with our previous studies on
the self-assembly of viologen or TTF-based tetrahedral radical
cation building blocks, illustrates the potential of the stacking of
conjugated radical cations in driving the formation of advanced
supramolecular architectures. In the future, we will design building
blocks that bear groups for the formation of reversible covalent
bonds, which can be tuned by the directed stacking of radical
cations.
The authors thank the National Natural Science Foundation of
China (Nos. 21172042 and J1103304), Science and Technology
Commission of Shanghai Municipality (13NM1400200), and the
Ministry of Science and Technology of the People’s Republic of
China (2013CB834501) for financial support of this work.
References and notes
1. (a) Lehn, J.-M. Polym. Int. 2002, 51, 825e839; (b) Brunsveld, L.; Folmer, B. J.
B.; Meijer, E. W.; Sijbesma, R. P. Chem. Rev. 2001, 101, 4071e4097; (c) Pal-
mans, A. R.; Meijer, E. W. Angew. Chem., Int. Ed. 2007, 46, 8948e8968; (d) De
Greef, T. F. A.; Smulders, M. M. J.; Wolffs, M.; Schenning, A. P. H. J.; Sijbesma,
R. P.; Meijer, E. W. Chem. Rev. 2009, 109, 5687e5754; (e) Chen, Y.; Liu, Y.
Chem. Soc. Rev. 2010, 39, 495e505; (f) Guo, D. S.; Liu, Y. Chem. Soc. Rev. 2012,
41, 5907e5921; (g) Chen, G.; Jiang, M. Chem. Soc. Rev. 2011, 40, 2254e2266;
(h) Liu, Y.; Wang, Z.; Zhang, X. Chem. Soc. Rev. 2012, 41, 5922e5932; (i)
Zheng, B.; Wang, F.; Dong, S.; Huang, F. Chem. Soc. Rev. 2012, 41, 1621e1636;
(j) Vukotic, V. N.; Loeb, S. J. Chem. Soc. Rev. 2012, 41, 5896e5906; (k) Li, S. L.;
Xiao, T.; Lin, C.; Wang, L. Chem. Soc. Rev. 2012, 41, 5950e5968; (l) Seiffert, S.;
Sprakel, J. Chem. Soc. Rev. 2012, 41, 909e930.
4. Experimental section
4.1. Synthesis and characterization of compound T1
2. (a) Aida, T.; Meijer, E. W.; Stupp, S. I. Science 2012, 335, 813e817; (b) Zhang, W.;
Jin, W.; Fukushima, T.; Saeki, A.; Seki, S.; Aida, T. Science 2011, 334, 340e343; (c)
Hashidzume, A.; Harada, A. Polym. Chem. 2011, 2, 2146e2154; (d) Appel, E. A.;
del Barrio, J.; Loh, X. J.; Scherman, O. A. Chem. Soc. Rev. 2012, 41, 6195e6214; (e)
Yan, X.; Wang, F.; Zheng, B.; Huang, F. Chem. Soc. Rev. 2012, 41, 6042e6065; (f)
Wang, F.; Han, C.; He, C.; Zhou, Q.; Zhang, J.; Wang, C.; Li, N.; Huang, F. J. Am.
Chem. Soc. 2008, 130, 11254e11255; (g) Ge, Z.; Hu, J.; Huang, F.; Liu, S. Angew.
Chem., Int. Ed. 2009, 48, 1798e1802; (h) Yan, X.; Xu, D.; Chi, X.; Chen, J.; Dong,
S.; Ding, X.; Yu, Y.; Huang, F. Adv. Mater. 2012, 24, 362e369; (i) Zhang, M.; Xu,
D.; Yan, X.; Chen, J.; Dong, S.; Zheng, B.; Huang, F. Angew. Chem., Int. Ed. 2012, 51,
7011e7015; (j) Ji, X.; Yao, Y.; Li, J.; Yan, X.; Huang, F. J. Am. Chem. Soc. 2013, 135,
74e77; (k) Sun, R.; Xue, C.; Ma, X.; Gao, M.; Tian, H.; Li, Q. J. Am. Chem. Soc. 2013,
135, 5990e5993.
2-Iodo-tetrathiafulvalene (7, 33 mg, 0.1 mmol), Pd(PPh3)2Cl2
(2 mg, 0.0034 mmol), CuI (1 mg, 0.0057 mmol), and tetrakis(4-
ethynylphenyl)methane (3, 14 mg, 0.017 mmol) were dissolved in
the mixture of 4 mL of NEt3 and 4 mL of THF. Then the mixture was
degassed with N2. After stirring at 40 ꢃC over 24 h under N2 at-
mosphere, the mixture was cooled to room temperature and the
solvent was evaporated, the residue was dissolved in dichloro-
methane and filtered. Purification by column chromatography on
silica gel (hexane/dichloromethane 5:1 to 2:1, v/v, as eluent) fol-
lowed by recrystallization from ethanol gave T1 (5 mg) in 20% yield
3. (a) Ciesielski, A.; Schaeffer, G.; Petitjean, A.; Lehn, J.-M.; Samori, P. Angew. Chem.,
Int. Ed. 2009, 48, 2039e2043; (b) Lohmeijer, B. G. G.; Schubert, U. S. Angew. Chem.,
Int. Ed. 2002, 41, 3825e3829; (c) Hofmeier, H.; Schubert, U. S. Chem. Commun.
2005, 2423e2432; (d) Ligthart, G. B. W. L.; Ohkawa, H.; Sijbesma, R. P.; Meijer, E.
W. J. Am. Chem. Soc. 2005, 127, 810e811; (e) Scherman, O. A.; Ligthart, G. B.;
Sijbesma, R. P.; Meijer, E. W. Angew. Chem., Int. Ed. 2006, 45, 2072e2076; (f) Beck,
J. B.; Rowan, S. J. J. Am. Chem. Soc. 2003, 125, 13922e13923; (g) Ohga, K.; Taka-
shima, Y.; Takahashi, H.; Kawaguchi, Y.; Yamaguchi, H.; Harada, A. Macromole-
cules 2005, 38, 5897e5904; (h) Ikeda, M.; Tanaka, Y.; Hasegawa, T.; Furusho, Y.;
Yashima, E. J. Am. Chem. Soc. 2006, 128, 6806e6807; (i) Liu, Y.; Yu, Y.; Gao, J.;
Wang, Z.; Zhang, X. Angew. Chem., Int. Ed. 2010, 49, 6576e6579; (j) Guo, D. S.;
Chen, S.; Qian, H.; Zhang, H. Q.; Liu, Y. Chem. Commun. 2010, 2620e2622; (k)
Wang, F.; Zhang, J.; Ding, X.; Dong, S.; Liu, M.; Zheng, B.; Li, S.; Wu, L.; Yu, Y.;
Gibson, H. W.; Huang, F. Angew. Chem., Int. Ed. 2010, 49, 1090e1094; (l) Zhang, Z.;
Luo, Y.; Chen, J.; Dong, S.; Yu, Y.; Ma, Z.; Huang, F. Angew. Chem., Int. Ed. 2011, 50,
1397e1401; (m) Dong, S.; Luo, Y.; Yan, X.; Zheng, B.; Ding, X.; Yu, Y.; Ma, Z.; Zhao,
Q.; Huang, F. Angew. Chem., Int. Ed. 2011, 50, 1905e1909; (n) Rossow, T.; Hack-
elbusch, S.; van Assenbergh, P.; Seiffert, S. Polym. Chem. 2013, 4, 2515e2527; (o)
Kieltyka, R. E.; Pape, A. C. H.; Albertazzi, L.; Nakano, Y.; Bastings, M. M. C.; Voets, I.
K.; Dankers, P. Y. W.; Meijer, E. W. J. Am. Chem. Soc. 2013, 135, 11159e11164; (p)
Vatankhah-Varnoosfaderani, M.; Hashmi, S.; GhavamiNejad, A.; Stadler, F. J.
Polym. Chem. 2014, 5, 512e523.
as a yellow solid. FT-IR (n) 3070, 2964, 2923, 2198, 1629, 1492,
1384 cmꢂ1; 1H NMR (400 MHz, CDCl3)
d
7.35 (d, J¼8.0 Hz, 8H), 7.12
(d, J¼8.0 Hz, 8H), 6.54 (s, 4H), 6.33 (s, 8H); 13C NMR (100 MHz,
CDCl3)
d 146.4, 131.3, 131.0, 124.9, 120.4, 119.3, 119.0, 116.1, 113.4,
93.1, 81.2, 58.9; HRMS (ESI): calcd for C57H28S16, 1223.7722 [M]þ,
found: 1223.7725.
4.2. Synthesis and characterization of compound T2
Dissolve 2-(Ethoxycarbonyl)-tetrathiafulvalene (8, 110 mg,
0.4 mmol) in 15 mL of THF, to which 5 mL of 0.1 M NaOH aqueous
solution was added. The mixture was stirred at room temperature
until all of the compound 8 was consumed. Then 0.5 M of HCl
aqueous solution was added dropwisely until pH 7. The mixture
was extracted by dichloromethane and washed by 2ꢁ50 mL of
water. The organic layer was dried over anhydrous MgSO4 and the
solvent was removed under vacuum. To the residue dissolved in
10 mL of DMF were added EDCI (87 mg, 0.45 mmol), DMAP (55 mg,
0.45 mmol), and tetrakis(4-amino-phenyl)methane (6, 19 mg,
0.05 mmol) subsequently. The mixture was stirred at room tem-
perature for 5 days and the solvent was removed under vacuum,
the residue was recrystallized from dichloromethane to give T2
4. (a) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z.
R.; Bae, T. H.; Long, J. R. Chem. Rev. 2012, 112, 724e781; (b) Li, J. R.; Sculley, J.;
Zhou, H. C. Chem. Rev. 2012, 112, 869e932; (c) Seiffert, S. Angew. Chem., Int. Ed.
2013, 52, 11462e11468; (d) Rossow, T.; Seiffert, S. Polym. Chem. 2014, 5,
3018e3029; (e) Li, Z.-Y.; Zhang, Y.; Zhang, C.-W.; Chen, L.-J.; Wang, C.; Tan, H.;
Yu, Y.; Li, X.; Yang, H.-B. J. Am. Chem. Soc. 2014, doi:ja413047r; (f) Yan, X.; Cook,
T. R.; Pollock, J. B.; Wei, P.; Zhang, Y.; Yu, Y.; Huang, F.; Stang, P. J. J. Am. Chem.
Soc. 2014, 136, 4460e4463. doi:ja412249k.
(31 mg) in 48% yield as a red solid. FT-IR (
1637, 1596, 1508, 1405, 1322 cmꢂ1 1H NMR (400 MHz, DMSO-d6)
10.33 (s, 4H), 7.83 (s, 4H), 7.55 (d, J¼8.0 Hz, 8H), 7.07 (d, J¼8.0 Hz,
8H), 6.75 (s, 8H); 13C NMR (100 MHz, DMSO-d6)
157.4, 142.0, 139.1,
n) 3070, 2975, 2923, 2360,
5. El-Kaderi, H. M.; Hunt, J. R.; Mendoza-Cortes, J. L.; Cote, A. P.; Taylor, R. E.;
;
O’Keeffe, M.; Yaghi, O. M. Science 2007, 316, 268e272.
d
ꢀ
6. (a) Jerome, D. Chem. Rev. 2004, 104, 5565e5591; (b) Bendikov, M.; Wudl, F.;
Perepichka, D. F. Chem. Rev. 2004, 104, 4891e4945; (c) Lortz, R.; Wang, Y.;
d
€
Demuer, A.; Bottger, P.; Bergk, B.; Zwicknagl, G.; Nakazawa, Y.; Wosnitza, J.
136.1, 133.8, 130.6, 126.9, 120.3, 120.0, 119.4, 112.5, 107.0, 105.8, 42.0;
HRMS (ESI): calcd for 1/2 (C53H32N4O4S16), 649.8977 [M]2þ, found:
649.8986.
ꢀ
Phys. Rev. Lett. 2007, 99, 187002-1e187002-4; (d) Brunetti, F. G.; Lopez, J. L.;
Atienza, C.; Martín, N. J. Mater. Chem. 2012, 22, 4188e4205; (e) Fahrenbach, A.
C.; Warren, S. C.; Incorvati, J. T.; Avestro, A. J.; Barnes, J. C.; Stoddart, J. F.;

L. Chen et al. / Tetrahedron 70 (2014) 4778e4783
4783
Grzybowski, B. A. Adv. Mater. 2013, 25, 331e348; (f) Park, J. S.; Karnas, E.;
Ohkubo, K.; Chen, P.; Kadish, K. M.; Fukuzumi, S.; Bielawski, C. W.; Hudnall, T.
W.; Lynch, V. M.; Sessler, J. L. Science 2010, 329, 1324e1327; (g) Bejger, C.; Park,
J. S.; Silver, E. S.; Sessler, J. L. Chem. Commun. 2010, 7745e7747; (h) Flood, A. H.;
Nygaard, S.; Laursen, B. W.; Jeppesen, J. O.; Stoddart, J. F. Org. Lett. 2006, 8,
2205e2208; (i) Fahrenbach, A. C.; Zhu, Z.; Cao, D.; Liu, W. G.; Li, H.; Dey, S. K.;
Basu, S.; Trabolsi, A.; Botros, Y. Y.; Goddard, W. A., III; Stoddart, J. F. J. Am. Chem.
Soc. 2012, 134, 16275e16288.
Sarjeant, A. A.; Wasielewski, M. R.; Goddard, W. A., III; Stoddart, J. F. J. Am. Chem.
Soc. 2011, 133, 4538e4547.
10. (a) Chiang, P. T.; Chen, N. C.; Lai, C. C.; Chiu, S. H. Chem.dEur. J. 2008, 14,
6546e6552; (b) Zhou, C.; Tian, J.; Wang, J.-L.; Zhang, D.-W.; Zhao, X.; Liu, Y.; Li,
Z.-T. Polym. Chem. 2014, 5, 341e345.
11. Tian, J.; Ding, Y. D.; Zhou, T. Y.; Zhang, K. D.; Zhao, X.; Wang, H.; Zhang, D.-W.;
Liu, Y.; Li, Z.-T. Chem.dEur. J. 2014, 20, 575e584.
12. (a) Ganesan, P.; Yang, X.; Loos, J.; Savenije, T. J.; Abellon, R. D.; Zuilhof, H.;
€
7. (a) Wudl, F.; Smith, G. M.; Hufnagel, E. J. J. Chem. Soc., Chem. Commun. 1970,
1453e1454; (b) Torrance, J. B.; Scott, B. A.; Welber, B.; Kaufman, F. B.; Seiden, P.
E. Phys. Rev. B 1979, 19, 730e741.
Sudholter, E. J. R. J. Am. Chem. Soc. 2005, 127, 14530e14531; (b) Galoppini, E.;
Gilardi, R. Chem. Commun. 1999, 173e174.
13. (a) Green, D. C. J. Org. Chem. 1979, 44, 1476e1479; (b) Zhao, Y.-P.; Wu, L.-Z.; Si,
G.; Liu, Y.; Xue, H.; Zhang, L.-P.; Tung, C.-H. J. Org. Chem. 2007, 72, 3632e3639;
(c) Cooke, G.; Rotello, V. M.; Radhi, A. Tetrahedron Lett. 1999, 40, 8611e8613.
14. (a) Gomar-Nadal, E.; Mugica, L.; Vidal-Gancedo, J.; Casado, J.; Navarrete, J. T. L.;
Veciana, J.; Rovira, C.; Amabilino, D. B. Macromolecules 2007, 40, 7521e7531; (b)
Wang, W. K.; Chen, Y. Y.; Wang, H.; Zhang, D. W.; Liu, Y.; Li, Z. T. Chem.dAsian J.
2014, 9, 1039e1044.
15. (a) Yoshizawa, M.; Kumazawa, K.; Fujita, M. J. Am. Chem. Soc. 2005, 127,
13456e13457; (b) Wang, C.; Dyar, S. M.; Cao, D.; Fahrenbach, A. C.; Horwitz, N.;
Colvin, M. T.; Carmieli, R.; Stern, C. L.; Dey, S. K.; Wasielewski, M. R.; Stoddart, J.
F. J. Am. Chem. Soc. 2012, 134, 19136e19145.
8. Ziganshina, A. Y.; Ko, Y. H.; Jeon, W. S.; Kim, K. Chem. Commun. 2004, 806e807.
9. (a) Barin, G.; Coskun, A.; Friedman, D. C.; Olson, M. A.; Colvin, M. T.; Carmielli,
R.; Dey, S. K.; Bozdemir, O. A.; Wasielewski, M. R.; Stoddart, J. F. Chem.dEur. J.
2011, 17, 213e222; (b) Spruell, J. M.; Coskun, A.; Friedman, D. C.; Forgan, R. S.;
Sarjeant, A. A.; Trabolsi, A.; Fahrenbach, A. C.; Barin, G.; Paxton, W. F.; Dey, S. K.;
Olson, M. A.; Benítez, D.; Tkatchouk, E.; Colvin, M. T.; Carmielli, R.; Caldwell, S.
T.; Rosair, G. M.; Hewage, S. G.; Duclairoir, F.; Seymour, J. L.; Slawin, A. M. Z.;
Goddard, W. A., III; Wasielewski, M. R.; Cooke, G.; Stoddart, J. F. Nat. Chem. 2010,
2, 870e879; (c) Coskun, A.; Spruell, J. M.; Barin, G.; Fahrenbach, A. C.; Forgan, R.
S.; Colvin, M. T.; Carmieli, R.; Benitez, D.; Tkatchouk, E.; Friedman, D. C.;