Self-assembly of sulfur-containing heterocyclic compounds constructed by thianthrene units and their sulfonium salts

Article abstract of DOI:10.1002/hc.21459

The self-assembly of sulfur-containing heterocyclic compounds, 5,6,11,12,17,18-hexathia-5,6,11,12,17,18-hexahydrotrinaphthylene and 5,7,12,14-tetrathiapentacene having octyloxy groups 1 and 2, was examined. Sulfides 1 and 2 self-assembled to form fibrous

Full text of DOI:10.1002/hc.21459

Received: 26 September 2018
DOI: 10.1002/hc.21459
Revised: 30 October 2018
Accepted: 1 November 2018
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S P E C I A L I S S U E : A T R I B U T E T O P R O F E S S O R
N A O M I C H I F U R U K AWA O N T H E O C C A S I O N O F
H I S 8 2 N D B I R T H D AY - B Y I N V I T AT I O N O N LY
Self-assembly of sulfur-containing heterocyclic compounds
constructed by thianthrene units and their sulfonium salts
Kazunori Hirabayashi
Toshio Shimizu
Kenki Ebine
Youhei Kawabata
Yoshihiro Yoshida
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Department of Chemistry, Graduate School
of Science, Tokyo Metropolitan University,
Tokyo, Japan
Abstract
The self-assembly of sulfur-containing heterocyclic compounds, 5,6,11,12,17,18-he
xathia-5,6,11,12,17,18-hexahydrotrinaphthylene and 5,7,12,14-tetrathiapentacene
having octyloxy groups 1 and 2, was examined. Sulfides 1 and 2 self-assembled to
form fibrous materials. The methylation reactions of 1 and 2 proceeded to give mon-
omethylated sulfonium salts 3 and 4, and the self-assembly of 3 and 4 was also stud-
ied. Fibrous materials of sulfonium salts 3 and 4 were formed in hexane/CHCl3
solution. The structure of the fibrous material of 3 might be similar to that of the fi-
brous material of 1. The aggregation behavior of 1 and 3 in cyclohexane-d12 was
studied by VT 1H NMR measurements at various concentrations. VT 1H NMR meas-
urements revealed that the stacking structure of 1 was different from that of 3.
Correspondence
Toshio Shimizu, Department of Chemistry,
Graduate School of Science, Tokyo
Metropolitan University, Tokyo, Japan.
Email: shimizu-toshio@tmu.ac.jp
Sulfonium salts are useful as reaction reagents and reac-
tion intermediates and have attracted much attention for their
1
INTRODUCTION
|
In sulfur chemistry, many polythia-aromatic compounds have
attracted much attention because of their non-alternating spin
distribution patterns. 5,6,11,12,17,18-hexathia-5,6,11,12,17,
18-hexahydrotrinaphthylene and its derivatives were synthe-
sized, and spin multiplicity in the ground state was investi-
gated.[1] 5,7,12,14-tetrathiapentacene and its derivatives were
also studied.[2] However, further investigations of their ap-
plication in materials science have not been carried out. The
self-assembly of organic π-conjugated systems in solution
may be used to construct unique supramolecular structures.
Self-assembled molecules were constructed through weak
noncovalent interactions, including van der Waals interac-
tions, π-π stacking, charge transfer, and H-bonding interac-
tions.[3] Furthermore, self-assembly would depend on the
concentrations of the mixed solvents. The solubility of a mol-
ecule, which is affected by the length of the substituents, such
as an alkyl or alkoxyl group, is important for the formation of
a self-assembled molecule.[4] The self-assembly of organo-
sulfur compounds, such as TTF[5] and oligothiophene,[6] was
also investigated. Most of them were composed of sulfides.
potential applications in organic syntheses.[7] On the other
hand, the application of sulfonium salts in self-assembly
was investigated recently. It was reported that fibers were
formed by the self-assembly of polymers containing sulfo-
nium salts.[8] We herein report the syntheses and aggregation
behavior of 5,6,11,12,17,18-hexathia-5,6,11,12,17,18-hexah
ydrotrinaphthylene and 5,7,12,14-tetrathiapentacene having
long alkoxy side chains. In addition, their sulfonium salt de-
rivatives were investigated.
2
RESULTS AND DISCUSSION
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Compounds 1 and 2 were prepared from 4,5-dibromocatechol
as the starting compound, as shown in Scheme 1. The hy-
droxyl groups of 4,5-dibromocatechol were transformed into
octyloxy groups by the Williamson ether synthesis to give 5
in 77% yield.[9] The substitution reaction of 5 with cyclohex-
anethiol proceeded in the presence of copper(I) oxide to give
6 in 83% yield.[10] Cleavage of the sulfur-carbon bond was
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Heteroatom Chemistry. 2018;e21459.
https://doi.org/10.1002/hc.21459
wileyonlinelibrary.com/journal/hc
© 2018 Wiley Periodicals, Inc.
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CySH
Cu2O
OctBr
KOH
OctO
OctO
Br
Br
OctO
OctO
SCy
SCy
HO
HO
Br
Br
Na
Pyridine
reflux
20 h
NMP
150
15 h
DMSO
rt, 3 h
5 (77%)
6 (83%)
OctO
OOct
1) Na
2) C6Br6
S
S
S
S
DMF, reflux
24 h
S
S
OctO
OctO
OOct
OOct
OctO
OctO
SH
SH
1 (27%)
1) Na
7
OctO
OctO
S
S
S
S
OOct
OOct
2) 1,2,4,5-C6H2Br4
DMF, reflux
24 h
SCHEME 1 Synthesis of sulfides 1
and 2
2 (27%)
carried out by using sodium to give 7, which was used with-
out purification in the subsequent reactions.[11] The reactions
of 7 with aryl bromides were proceeded to give the corre-
sponding compounds with polymeric materials. Compounds
1 and 2 were obtained in higher yields when aryl bromides
were added to the thiolate solution three (in the case of hexa-
bromobenzene) or two (in the case of tetrabromobenzene)
times in separate portions than when aryl bromides were
added in one portion.
Methylation of 1 was investigated by using methyl triflu-
oromethanesulfonate as the methylation reagent, as shown in
Scheme 2. The reaction of 1 with 1 equiv. of methyl trifluo-
romethanesulfonate failed to produce a sulfonium salt. When
2 equiv. of methyl trifluoromethanesulfonate was used and
the hexane/CHCl3 solution of the crude product was allowed
to stand at 0°C, sulfonium salt 3 was obtained as a solid in
79% yield. As mentioned below, the solid was found to be
aggregates. In the case of 2, monomethylated product 4 was
also produced by using 2 equiv. of methyl trifluoromethane-
sulfonate. After the reaction, the obtained solid was washed
with diethyl ether to give 4 in 65% yield.
OctO
OOct
MeOTf
+
-
S
S
S Me
1
CH2Cl2, rt
144 h
S
S
OctO
OctO
S
OOct
OOct
3 (79%)
-
Me
S
+
OctO
OctO
S
S
OOct
OOct
MeOTf
2
CH2Cl2, rt
96 h
S
4 (65%)
SCHEME 2 Methylation of sulfides 1 and 2
peaks at a lower angle were found, which indicated the for-
mation of large aggregation structure of each molecule. As
shown in Figure 1D, the XRD pattern of the nanoscale hol-
low spheres obtained from sulfide 1 in hexane has three
refraction peaks at lower angles of 2θ = 3.80° (correspond-
ing to 22.7 Å), 5.08° (17.0 Å), and 7.18° (12.0 Å), which
are ascribed to the refractions from the (020), (1-11), and
(1-13) planes. These diffraction results could be assigned
to the refractions from a face-centered orthorhombic lat-
tice with lattice parameters of a = 20.21, b = 46.49, and
c = 49.58 Å.
The self-assembly of sulfides 1 and 2 was examined.
White fibrous materials were formed when a hexane solu-
tion of sulfide 1 (3.1 mol/L) was allowed to stand at 0°C
for 1 hour. Then, the self-assembly behavior of 1 in other
solvents was investigated. Fibrous materials were also
formed in hexane/CHCl3 (v/v = 20/1) and hexane/toluene
(v/v = 20/1). Their SEM images are shown in Figures 1A-
C. The fibers in hexane were 200-1200 nm wide. From the
SEM images of the two other cases, ribbon-like fibers were
apparent and the fibers were wider than those obtained in
hexane. Then, the internal structure of the fibrous materials
of sulfide 1 in hexane was investigated by XRD. Diffraction
In the case of sulfide 2, fibrous materials were also formed
when a hexane/CHCl3 (v/v = 20/1) solution of 2 was left to

HIRABAYASHI et Al.
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(A)
(B)
1.42 µm
4.00 µm
(C)
(D)
4000
3000
2000
1000
2.32 µm
0
3
5
7
9
2
FIGURE 1 SEM images of fibrous materials of sulfide 1: A, in hexane; B, in hexane/CHCl3 (v/v = 20/1); C, in hexane/toluene (v/v = 20/1).
D, XRD pattern of fibrous materials of sulfide 1 in hexane
(A)
(B)
10000
8000
6000
4000
2000
0
5.26 µm
FIGURE 2 A, SEM image and B,
XRD pattern of fibrous materials of sulfide
2 in hexane/CHCl3 (v/v = 20/1)
5
7
3
9
2
stand at 0°C for 1 hour, and the widths were 500-1500 nm, as
estimated from the SEM image (Figure 2A). The XRD pat-
tern of the nanoscale hollow spheres formed from sulfide 2 in
hexane/CHCl3 shows several refraction peaks at 2θ = 3.28°
(corresponding to 27.3 Å), 3.82° (23.4 Å), 4.66° (19.2 Å),
5.14° (16.4 Å), 6.32° (14.2 Å), and 8.36° (10.7 Å), which are
ascribed to the refractions from the (110), (020), (001), (200),
(111), and (130) planes (Figure 2B). These diffraction results
could be assigned to the refractions from a base-centered
monoclinic lattice with lattice parameters of a = 36.24,
b = 45.78, c = 20.11 Å, and β = 109.34°.
The self-assembly of sulfonium salts 3 and 4 was also
investigated. When a solution of sulfonium salt 3 in hexane/
CHCl3 (v/v = 100/1) was allowed to stand at 0°C for 1d,
green fibrous materials were formed. The SEM image of the
green fibrous materials is shown in Figure 3A. The fibers
were 700-1200 nm wide. The XRD pattern of the nanoscale
hollow spheres obtained from sulfonium salt 3 shows a

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(A)
(B)
500
400
300
200
100
0
3.33 µm
2
4
6
8
10
2
(C)
(D)
25000
20000
15000
10000
5000
0
FIGURE 3 A, SEM image and B,
XRD pattern of fibrous materials of sulfide
3 in hexane/CHCl3 (v/v = 100/1). C, SEM
image and (D) XRD pattern of fibrous
materials of sulfide 4 in hexane/CHCl3
(v/v = 20/1)
2.43 µm
2
4
6
8
10
2
weak, broad refraction peak at 2θ = 3.74° (corresponding to
23.1 Å) (Figure 3B), which is almost the same as that of the
fibrous materials of sulfide 1. Thus, the fibrous materials
of sulfonium salt 3 had similar stacking structures to those
of sulfide 1. Fibrous materials obtained from a solution of
sulfonium salt 4 in hexane/CHCl3 (v/v = 20/1) were a white
solid. The fibers were 800-1600 nm wide (Figure 3C). The
XRD pattern of the fibrous materials of sulfonium salt 4
shows only one refraction peak at 2θ = 3.00° in the lower
angle region (corresponding to 28.8 Å) (Figure 3D). From
these results, the methylation of sulfide 2 could lead to a
dramatic change of the fiber structure of sulfonium salt
4 although the structure of sulfonium salt 4 could not be
assigned.
shown in Figure 4. The chemical shifts were found to be
affected by the concentration. Thus, the aggregation behav-
ior of sulfide 1 and sulfonium salt 3 in cyclohexane-d12
was confirmed. In the case of sulfide 1, an upfield shift
was observed at higher concentration, indicating that pro-
ton Ha might be located around the shielding zone of one
of the benzene rings. In contrast, in the case of sulfonium
salt 3, a downfield shift was observed at higher concentra-
tion, indicating that proton Hb might be located directly
above the deshielding zone and the aromatic ring of 3 was
stacked with same direction. Furthermore, taking the XRD
results into consideration, the stacking of sulfide 1 might
take place regularly with a partial slip. On the other hand,
in the case of sulfonium salt 3, the methyl group on the sul-
fur atom might inhibit the shifting of molecules and might
direct without regularity.
The aggregation behavior of sulfide 1 and sulfonium
salt 3 in solution was investigated on the basis of the con-
centration dependence of the 1H NMR chemical shifts. The
1H NMR spectra of 1 and 3 in chloroform-d were measured
at different concentrations (4.0 and 32.0 mmol/L). No
3
CONCLUSION
|
1
changes of chemical shifts of the H NMR signals were
observed. Thus, the chemical shifts were not affected by
concentration and the compounds existed as monomers in
5,6,11,12,17,18-hexathia-5,6,11,12,17,18-hexahydrotrinap
hthylene and 5,7,12,14-tetrathiapentacene having octyloxy
groups 1 and 2 and their monomethylated sulfonium salts
3 and 4 were synthesized. These compounds aggregated to
afford fibrous materials. The stacking structures of fibrous
1
chloroform-d solution. Next, VT H NMR spectra were
measured in cyclohexane-d12 at various concentrations and
the chemical shifts of protons Ha and Hb were plotted, as

HIRABAYASHI et Al.
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otherwise noted, commercially available reagents were used
without purification.
(A)
6.98
OctO
S
OOct
Ha
6.96
6.94
6.92
6.90
4.2
1,2-Dibromo-4,5-bis(octyloxy)benzene (5)
|
333 K
323 K
To a suspended solution of catechol (4.02 g, 15.0 mmol)
and potassium hydroxide (3.38 g, 60.3 mmol) in N,N-
dimethylformaldehyde (15 mL) was added 1-bromooctane
(5.20 mL, 30.0 mmol) at 0°C. The reaction mixture was stirred
at room temperature for 3 hours. To the reaction mixture was
added water (20 mL). The product was extracted with diethyl
ether (30 mL × 3). The combined extracts were washed with
brine (20 mL) and dried over magnesium sulfate. After filtra-
tion, the solution was concentrated in vacuo. The residue was
purified by flash column chromatography on silica gel (hex-
ane/ethyl acetate = 50/1) to give 5 in 77% yield as a colorless
solid. Product 5 was identical with the authentic sample.[12] Mp
S
313 K
303 K
298 K
0
10
20
30
40
Concentration (mM)
(B)
10.5
OctO
S
OOct
Hb
298 K
303 K
313 K
323 K
333 K
9.5
8.5
7.5
6.5
1
+
40-42°C. H NMR (400 MHz, CDCl3) δ 0.87 (t, J = 6.9 Hz,
S Me
6H), 1.28-1.47 (m, 20H), 1.78 (tt, J = 6.9, 6.9 Hz, 4H), 3.94 (t,
J = 6.9 Hz, 4H), 7.06 (s, 2H). 13C NMR (100 MHz, CDCl3) δ
14.4, 22.9, 26.2, 29.3, 29.4, 29.5, 32.0, 69.8, 114.7, 118.0, 149.0.
IR (ATR) νμαξ 2921, 1496, 1247, 1195, 845 cm−1. Anal. Calcd
for C22H36Br2O2: C, 53.67; H, 7.37. Found: C, 53.40; H, 7.21.
0
10
20
30
40
Concentration (mM)
4.3
1,2-Bis(cyclohexylthio)-4,5-
FIGURE 4 Concentration dependence of 1H NMR chemical
shifts in cyclohexane-d12 at variable temperature: A, for Ha of sulfide 1
and B, for Hb of sulfonium salt 3
|
bis(octyloxy)benzene (6)
To a suspended solution of 5 (2.96 g, 10.0 mmol) and
copper(I) oxide (1.43 g, 20.0 mmol) in N-methylpyrrolidone
(40 mL) was added cyclohexanethiol (2.50 mL, 20.0 mmol)
at room temperature. The reaction mixture was stirred at
150°C for 16 hours. To the reaction mixture was added 1 M
HCl aq. (20 mL). The product was extracted with diethyl ether
(30 mL × 3). The combined extracts were washed with brine
(20 mL) and dried over magnesium sulfate. After filtration,
the solution was concentrated in vacuo. The residue was puri-
fied by flash column chromatography on silica gel (hexane/
ethyl acetate = 20/1) to give 6 in 83% yield as a pale yellow
1
materials 1, 2, and 3 were estimated by XRD and/or VT H
NMR measurements.
4
EXPERIMENTAL SECTION
General
|
4.1
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All reactions were carried out under a nitrogen atmosphere.
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra
were measured on a JEOL JNM-EX-400 FT NMR sys-
tem as CDCl3 or CD3CN solution. Chemical shifts were
1
oil. H NMR (400 MHz, CDCl3) δ 0.88 (t, J = 6.8 Hz, 6H),
1.22-1.50 (m, 30H), 1.59-1.63 (m, 2H), 1.72-1.83 (m, 8H),
1.91-1.99 (m, 4H), 3.11 (tt, J = 3.5, 10.6 Hz, 2H), 3.97 (t,
J = 6.8 Hz, 4H), 6.95 (s, 2H). 13C NMR (100 MHz, CDCl3)
δ 14.2, 22.8, 26.0, 26.1, 26.2, 29.36, 29.38, 29.5, 31.9, 33.3,
46.9, 69.6, 118.8, 129.5, 148.3. IR (ATR) νμαξ 2923, 1465,
1244, 1197 cm−1. MS (APCI-TOF) positive: m/z = 562
([M + H]+). Anal. Calcd for C34H58O2S2: C, 72.54; H, 10.39.
Found: C, 72.77; H, 10.54.
1
expressed in ppm with TMS (0.0 ppm for H) or CDCl3
(77.0 ppm for 13C) as the internal standard. Infrared (IR)
spectra were measured on a PerkinElmer Spectrum Two IR
spectrometer. Elemental analyses were carried out with an
Exeter Analytical, Inc. CE-440 Elemental Analyzer. Thin
layer chromatography (TLC) was performed on Merck TLC
Silica Gel 60F254 Plates. Flash column chromatography was
carried out using Kanto Chemical Silica Gel 60 N (spheri-
cal, neutral, 63-210 m). X-ray powder diffraction (XRD)
analysis was performed with a Rigaku RINT TTR III dif-
fractometer with Cu Kα radiation. SEM observations were
carried out under a KEYENCE VE-9800 microscope. Unless
4.4
(7)
4,5- Bis(octyloxy)benzene-1,2-dithiol
|
To a solution of 6 (1.61 g, 2.86 mmol) in pyridine (15 mL)
were added slowly small pieces of sodium lump (0.50 g,

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21.8 mmol) at room temperature. The reaction mixture was
stirred at 115°C for 20 hours. To the reaction mixture was
added 1 M HCl aq. (30 mL). The product was extracted
with diethyl ether (30 mL × 3). The combined extracts were
washed with brine (20 mL) and dried over magnesium sul-
fate. After filtration, the solution was concentrated in vacuo
to give a brown oil (0.66 g). The residue was used without
purification because the corresponding dithiols were con-
verted into disulfides during purification.
Calcd for C50H74O4S4: C, 69.24; H, 8.60. Found: C, 68.80;
H, 8.56.
4.6
Syntheses of sulfonium salts 3 and 4
|
To a solution of sulfide (0.04 mmol) in dichlorometh-
ane (2 mL) was added methyl trifluoromethanesulfonate
(8.70 μL, 0.08 mmol) at room temperature. The reaction
mixture was stirred at room temperature. The solvent was re-
moved to give a brown solid. The obtained solid was washed
with acetone. The filtrate was concentrated in vacuo to give
a brown solid.
4.5
Syntheses of 1 and 2
|
To a solution of crude product 7 (1.16 g) in dimethylformal-
dehyde (15 mL) were added slowly small pieces of sodium
lump (0.16 g, 6.86 mmol) at room temperature. The reaction
mixture was stirred at room temperature for 20 hours. After
the sodium lumps disappeared, hexabromobenzene (0.47 g,
0.86 mmol) in three portions or 1,2,4,5-tetrabromobenzene
(0.51 g, 1.30 mmol) in two portions was added to the re-
sulting solution. The reaction mixture was stirred at 150°C
for 24 hours. To the reaction mixture was added water
(10 mL) and the product was extracted with dichloromethane
(30 mL × 3). The combined extracts were washed with brine
(20 mL) and dried over magnesium sulfate. After filtration,
the solution was concentrated in vacuo. The residue was puri-
fied by flash column chromatography on silica gel (hexane/
ethyl acetate) to give the corresponding product.
4.6.1
2,3,8,9,14,15-Hexa(octyloxy)-
|
5-methyl-5,6,11,12,17,18-hexathia-
5,6,11,12,17,18-hexahydrotrinaphthylenium
trifluoromethanesulfonate (3)
The reaction mixture was stirred for 144 hours. After con-
centration, the brown solid was dissolved in chloroform/hex-
ane (chloroform/hexane = 1:100). The solution was allowed
to stand at 0°C to give 3 in 79% yield as a green solid. Mp
45.0-48.0°C (decomp.). 1H NMR (400 MHz, CDCl3) δ 0.87-
0.90 (m, 18H), 1.29-1.90 (m, 72H), 3.29 (s 3H), 3.98-4.14
(m, 12H), 7.06 (s, 1H), 7.08 (s, 1H), 7.09 (s, 1H), 7.19 (s,
1H), 7.33 (s, 1H), 8.03 (s, 1H). 13C NMR (100 MHz, CDCl3)
δ 14.0, 22.6, 25.8, 29.0, 29.16, 29.22, 29.6, 31.7, 69.4, 107.0,
113.7, 113.8, 117.4, 119.0, 122.2, 123.0, 123.2, 124.5, 124.6,
125.4, 125.7, 127.2, 134.6, 134.9, 135.2, 138.9, 143.3, 149.3,
149.8, 149.9, 150.3, 150.4, 153.5. IR (ATR) νμαξ 2924,
2855, 1500, 1466, 1255, 1205, 1171, 1027, 636 cm−1. ESI
MS (MeCN) positive: m/z = 1275.6 ([M-TfO]+); negative:
m/z = 149.0 (TfO−). Anal. Calcd for C74H111F3O9S7: C,
62.32; H, 7.85. Found: C, 62.42; H, 8.02.
4.5.1
2,3,8,9,14,15-Hexa(octyloxy)-
|
5,6,11,12,17,18-hexathia-5,6,11,12,17,18-
hexahydrotrinaphthylene (1)
1
27% yield. Pale yellow solid. Mp 54.0-56.0°C. H NMR
(400 MHz, CDCl3) δ 0.88 (t, J = 7.0 Hz, 18H), 1.22-1.50
(m, 60H), 1.81 (tt, J = 7.0, 7.0 Hz, 12H), 3.98 (t, J = 7.0 Hz,
12H), 7.08 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 14.3,
22.8, 26.1, 29.2, 29.4, 29.5, 32.0, 69.7, 114.1, 126.1, 135.2,
149.6. IR (ATR) νμαξ 2921, 1463, 1252, 1120, 845 cm−1.
UV (dichloromethane) λμαξ 266 (ε 1.24 × 104). MS (APCI-
TOF) positive: m/z = 1261 ([M + H]+). Anal. Calcd for
C72H108O6S6: C, 68.52; H, 8.63. Found: C, 68.60; H, 8.56.
4.6.2
5-Methyl-2,3,9,10-tetra(octyloxy)-
|
5,7,12,14-tetrathiapentacenium
trifluoromethanesulfonate (4)
The reaction mixture was stirred for 96 hours. After concentra-
tion, the brown solid was washed with diethyl ether to give 4 in
65% yield as a white solid. Mp 73-75°C (decomp.). 1H NMR
(400 MHz, CD3CN) δ 0.85-0.89 (m, 12H), 1.27-1.44 (m, 40H),
1.74 (tt, J = 6.4 Hz, 8H), 3.05 (s, 3H), 3.96 (t, J = 6.4 Hz, 4H),
4.01-4.11 (m, 4H), 7.05 (s, 1H), 7.06 (s, 1H), 7.38 (s, 1H),
7.47 (s, 1H), 7.98 (s, 1H), 8.06 (s, 1H). 13C NMR (100 MHz,
CDCl3) δ 14.1, 22.6, 25.9, 28.8, 29.0, 29.22, 29.28, 31.8, 69.7,
108.1, 113.0, 113.8, 113.9, 116.4, 118.2, 123.4, 124.5, 127.2,
128.5, 131.6, 134.9, 139.1, 145.3, 149.6, 150.0, 150.3, 153.5.
IR (ATR) νμαξ 2923, 2849, 1495, 1251, 1201, 1021, 843 cm−1.
ESI MS (MeCN) positive: m/z = 881.4 ([M-TfO]+); negative:
m/z = 149.0 (TfO−). Anal. Calcd for C52H77F3O7S5: C, 60.55;
H, 7.52. Found: C, 60.90; H, 7.81.
4.5.2
2,3,9,10-Tetra(octyloxy)-5,7,12,14-
|
tetrathiapentacene (2)
27% yield. White solid. Mp 121.0-122.0°C. 1H NMR
(400 MHz, CDCl3) δ 0.85-0.90 (m, 12H), 1.28-1.45 (m,
40H), 1.79 (tt, J = 6.2, 6.2 Hz, 8H), 3.95 (t, J = 6.2 Hz, 8H),
6.96 (s, 4H), 7.57 (s, 2H). 13C NMR (100 MHz, CDCl3) δ
14.2, 22.8, 26.0, 29.2, 29.3, 29.4, 31.9, 69.6, 114.1, 126.3,
128.1, 136.1, 149.1. IR (ATR) νμαξ 2922, 2850, 1495, 1251,
843 cm−1. UV (dichloromethane) λμαξ 246 (ε 5.89 × 104).
MS (APCI-TOF) positive: m/z = 867.5 ([M + H]+). Anal.

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ORCID
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How to cite this article: Hirabayashi K, Ebine K,
Kawabata Y, Yoshida Y, Shimizu T. Self-assembly of
sulfur-containing heterocyclic compounds constructed
by thianthrene units and their sulfonium salts.
Heteroatom Chem. 2018;e21459. https://doi.org/
10.1002/hc.21459
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