Synthesis, Crystal Structures, and Solid-State Polymerization of 8?[4-(Dimethylamino)phenyl]octa-5,7-diynyl Carbamates

Article abstract of DOI:10.1021/acs.cgd.8b00815

Six butadiyne monomers with (dimethylamino)phenyl and N-substituted urethane substituents were synthesized and their crystal structures and solid-state polymerization were investigated. In five of the six monomers, directions of the butadiyne stacking and

Full text of DOI:10.1021/acs.cgd.8b00815

Article
pubs.acs.org/crystal
Cite This: Cryst. Growth Des. XXXX, XXX, XXX−XXX
Synthesis, Crystal Structures, and Solid-State Polymerization of 8‑[4-
(Dimethylamino)phenyl]octa-5,7-diynyl Carbamates
Masataka Ikeshima,† Hiroshi Katagiri,†,‡ Wataru Fujiwara,† Shizuo Tokito,†,‡ and Shuji Okada*,†,‡
†Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510, Japan
‡Graduate School of Organic Materials Science, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510, Japan
S
* Supporting Information
ABSTRACT: Six butadiyne monomers with (dimethylamino)phenyl and N-substituted urethane substituents were synthesized
and their crystal structures and solid-state polymerization were investigated. In five of the six monomers, directions of the
butadiyne stacking and the intermolecular hydrogen bonding between urethane groups coincided, and translational distance d
between adjacent butadiyne moieties was around 5 Å. Among them, four monomers showed angle θ between the translation
axis of the monomers and the butadiyne moiety of around 45°, which is appropriated for regular 1,4-addition polymerization.
These geometries resulted in formation of polydiacetylenes with characteristic excitonic absorption and relatively high
conversion. One monomer was found to have large θ, and the regular polymerization was not recognized to be quite low
conversion. However, in the remaining one monomer among six, the directions of butadiyne stacking and intermolecular
hydrogen bonding were different and d was much longer than 5 Å. However, distance between reacting carbons for 1,4-addition
was short enough resulting in comparable conversion without regular polymerization. Although introduction of urethane group
is effective to increase probability of the solid-state polymerization of butadiynes, hydrogen bonding direction, methylene chain
conformation, and disorder of the aromatic rings were found to afford the variation from the appropriate conditions.
two adjacent butadiyne monomers along the translation
direction, i.e., the polymerization direction, is about 5 Å, and
the angle θ between the translation direction and the linear
butadiyne moiety is about 45°.36,37 As materials for electronics
and photonics, control of the electronic state is an important
issue, and introduction of conjugated substituents is one of the
general strategies. However, butadiyne derivatives with directly
bound conjugated substituents often do not polymerize in their
crystalline states because many of the monomer alignments in
the crystals are out of polymerizable conditions. In order to
increase probability of topochemical polymerization of these
derivatives, we have introduced specific substituents taken
from symmetrically substituted polymerizable monomers as
one of the butadiyne substituents.38,39 For example, polymer-
izable butadiyne monomers have been obtained by introducing
INTRODUCTION
■
π-Conjugated polymers have been investigated as materials for
a variety of electronic and optical functions such as electrical
conduction,1−3 optical nonlinearlity,4−6 electrolumines-
cence,7−9 electric amplification by field-effect transistors,10−13
photovoltaics,14−17 etc. Among various π-conjugated polymers,
polydiacetylenes (PDAs) are quite unique in their preparation
process, i.e., topochemical polymerization of butadiyne
derivatives.18 Except for butadiyne derivatives, limited
monomers can be polymerized in the solid state, e.g.,
compounds with two CC bonds to show [2 + 2]
photocycloaddition reactions,19−24 butadienes,25−30 hexa-
triene,31 hexatriyne,32 and quinodimethanes.33−35 In the
crystals, all these monomers should take the proper polymer-
izable arrangement in which distances between intermolecular
reacting atoms are within the mobile ranges, and the case of
butadiynes is as well. As shown in Figure 1, the appropriate
conditions of the monomer arrangement for the polymer-
ization have been reported as follows: The distance d between
Received: May 29, 2018
Revised: August 17, 2018
Published: September 7, 2018
© XXXX American Chemical Society
A
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
was investigated in relation to the crystal structure. Optical and
electronic properties of the polymers were also examined.
EXPERIMENTAL SECTION
■
Starting materials, which are not specifically stated, were commercially
available and used without further purifications. DMAP butadiyne
derivatives were prepared according to the scheme in Figure 3. Details
of the synthesis procedures are described below.
2-Methyl-4-[4-(dimethylamino)phenyl]-3-butyn-2-ol 2. 4-
Bromo-N,N-dimethylaniline 1 (4.00 g, 20 mmol) and 2-methyl-3-
butyn-1-ol (2.02 g, 24 mmol) were added to triethylamine (60 mL)
and dissolved at 60 °C. Then, tetrakis(triphenylphosphine)-
palladium(0) (462 mg, 0.4 mmol) and copper(I) iodide (152 mg,
0.8 mmol) were added. After stirring the mixture for 24 h, it was
concentrated by the solvent evaporation, and the residue was purified
by column chromatography (silica gel, dichloromethane) to give 1.95
g (48%) of 2 as a pale green solid. IR (KBr) 3338, 2981, 2223, 1612,
1525, 813 cm−1; 1H NMR (400 MHz, CDCl3) δ = 1.60 (6H, s), 2.05
(1H, s), 2.96 (6H, s), 6.61 (2H, d, J = 7.9 Hz), 7.28 (2H, d, J = 7.9
Hz); 13C NMR (100 MHz, CDCl3) δ = 31.63, 40.18, 65.67, 82.91,
91.46, 109.45, 111.70, 132.65, 150.00.
4-Ethynyl-N,N-dimethylaniline 3. Compound 2 (2.03g, 10
mmol) and pulverized potassium hydroxide (561 mg, 10 mmol) were
added to toluene (50 mL), and the mixture was refluxed for 2 h under
a nitrogen atmosphere. The reactant was filtered, and solvent in the
filtrate was removed under reduced pressure. The residue was purified
by column chromatography (silica gel, hexane−dichloromethane
(4:1)) to give 950 mg (65%) of 3 as a pale yellowish green solid. IR
(KBr) 3291, 2952, 2123, 1604, 1517, 817 cm−1; 1H NMR (400 MHz,
CDCl3) δ = 1.56 (1H, s) 2.97 (6H, s), 6.60 (2H, d, J = 7.9 Hz), 7.38
(2H, d, J = 7.9 Hz); 13C NMR (100 MHz, CDCl3) δ = 40.14, 74.74,
84.81, 108.64, 111.61, 133.15, 150.31.
Figure 1. Solid-state polymerization scheme of butadiyne derivatives.
Geometric parameters of optimal monomer alignment for the
polymerization are d ≈ 5 Å and θ ≈ 45°.
urethane group forming intermolecular hydrogen bonding in
both substituents40,41 or even in one of two substituents.42−44
In our previous studies, we synthesized butadiyne derivatives
substituted by 4-(carbazol-9-yl)phenyl (CP) or (9-phenyl)-
carbazol-3-yl (PC) group to obtain PDAs with small ionization
potentials,45,46 which were potential materials for hole-
injection electrodes. Since hole injection and transport
properties of the PDAs seems to be strongly affected by the
highest occupied molecular orbital (HOMO) levels of the
corresponding monomers, monomers with a smaller ionization
potential are worth investigating. Thus, calculation of the
HOMO levels of some model compounds using the Gaussian
09 program,47 in which the molecular structure optimization
and HOMO energy level calculation were carried out at the
B3LYP/6-31G(d) and B3LYP/6-311+G(d,p) levels, respec-
tively, were conducted. For the three compounds (R = Me) in
Figure 2, i.e., penta-1,3-diyne derivatives substituted by (a) CP,
8-[4-(N,N-Dimethylamino)phenyl]octa-5,7-diyn-1-ol 4. To
the mixture of 3 (1.02 g, 7 mmol), copper(I) chloride (35 mg, 0.35
mmol), butylamine (30 mL), and methanol (15 mL), a small amount
of hydroxylamine hydrochloride was added so as that the color of the
mixture became yellow under a nitrogen atmosphere. To this mixture,
6-bromohex-5-yn-1-ol50 (1.24 g, 7 mmol) in butylamine (20 mL) and
methanol (10 mL) was added dropwise at ambient temperature for
1.5 h. When the color of the mixture became dark, an appropriate
amount of hydroxylamine hydrochloride was added until the color
turned to yellow. After addition completion, the mixture was further
stirred overnight. Solvent in the mixture was removed under reduced
pressure, and the residue was purified by column chromatography
(silica gel, dichloromethane) to give 1.15 g (51%) of 4 as a pale
yellow solid. IR (KBr) 3232, 2937, 2861, 2235, 2132, 1602, 1521, 813
1
cm−1; H NMR (500 MHz, CDCl3) δ = 1.61−1.76 (4H, m), 2.40
(2H, t, J = 6.8 Hz), 2.97 (6H, s), 3.69 (2H, t, J = 6.2 Hz), 6.59 (2H, d,
J = 9.1 Hz), 7.35 (2H, d, J = 9.1 Hz), the hydroxyl proton was not
clearly observed; 13C NMR (100 MHz, CDCl3) δ = 19.40, 24.64,
31.74, 40.07, 62.32, 65.95, 72.20, 76.47, 83.06, 108.11, 111.59, 133.70,
150.31
General Synthetic Procedure of 8-[4-(N,N-Dimethylamino)-
phenyl]octa-5,7-diynyl (N-Substituted Carbamate) 5a−5f.
Compound 4 (1.0 mmol) was dissolved in toluene (20 mL) at 60
°C under a nitrogen atmosphere, and dibutyltin dilaurate (3 drops)
and then isocyanate (1.1 mmol) were added dropwise. After stirring
the mixture for 1 day, its solvent was evaporated and the concentrated
residue was purified by a silica-gel column chromatography (silica gel,
dichloromethane or dichloromethane-hexane mixture depending on
compounds) and finally recrystallized from acetone−hexane mixture
to give the corresponding carbamate as colorless crystals.
8-[4-(N,N-Dimethylamino)phenyl]octa-5,7-diynyl N-Phenylcar-
bamate 5a. Yield 90%; mp 108 °C; IR (KBr) 3336, 2962, 2857,
2857, 2238, 2152, 1706, 1606, 1245, 815 cm−1; 1H NMR (500 MHz,
CDCl3) δ = 1.68 (2H, m), 1.83 (2H, m), 2.43 (2H, t, J = 7.1 Hz),
2.98 (6H, s), 4.20 (2H, t, J = 6.5 Hz), 6.58 (1H, br s), 6.59 (2H, d, J =
9.1 Hz,), 7.06 (1H, t, J = 7.1 Hz), 7.27−7.41 (6H, m); 13C NMR
(100 MHz, CDCl3) δ = 18.82, 24.35, 27.53, 39.57, 65.33, 66.86,
Figure 2. Butadiyne derivatives with an electron-donating aromatic
ring: (a) CP, (b) PC, and (c) DMAP derivatives. For calculations,
substituent R of the model compounds was set to methyl group. In
(c), acetylenic carbons are numbered for explanation of Table 3.
(b) PC, and (c) 4-(dimethylamino)phenyl (DMAP) groups,
the HOMO energies obtained were −5.70, −5.55, and −5.24
eV, respectively. As was expected from the chemical structures,
the DMAP derivative has higher HOMO energy because of the
substitution by the dimethylamino group with a stronger
electron donating feature. Although some butadiyne deriva-
tives with a DMAP group have been prepared and polymerized
in the solid state,48,49 the relationship between crystal
structures and polymerizability has never been reported. In
the present study, we synthesized six DMAP butadiyne
derivatives with a urethane group. We succeeded to analyze
their crystal structures, and polymerizability in the solid state
B
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 3. Synthesis scheme of [4-(dimethylamino)phenyl]butadiyne derivatives 5a−5f.
72.34, 75.76, 82.30, 108.56, 111.10, 118.39, 122.87, 128.53, 133.23,
139.34, 149.85, 153.23. Found: C, 76.47; H, 6.74; N, 7.78%. Calcd for
C23H24N2O2: C, 76.64; H, 6.71; N, 7.77%.
8-[4-(N,N-Dimethylamino)phenyl]octa-5,7-diynyl N-Phenethyl-
carbamate 5f. Yield 82%; mp 116 °C; IR (KBr) 3343, 3027, 2938,
2237, 2134, 1687, 1604, 1536, 1444, 1361, 1284, 1253, 1201, 1143,
1
8-[4-(N,N-Dimethylamino)phenyl]octa-5,7-diynyl N-[4-
(Trifluoromethyl)phenyl]carbamate 5b. Yield 58%; mp 163 °C; IR
(KBr) 3330, 2964, 2896, 2237, 2132, 1697, 1606, 1540, 1365, 1328,
1095, 1029, 946, 817, 748, 698, 528 cm−1; H NMR (500 MHz,
CDCl3) δ = 1.61 (2H, m), 1.74 (2H, m), 2.38 (2H, t, J = 6.8 Hz),
2.81 (2H, t, J = 6.8 Hz), 2.97 (6H, s), 3.44 (2H, dt, J = 6.1, 6.1 Hz),
4.08 (2H, t, J = 6.1 Hz), 4.69 (1H, br t), 6.58 (2H, d, J = 8.5 Hz),
7.13−7.27 (3H, m), 7.28−7.37 (4H, m); 13C NMR (125 MHz,
CDCl3) δ = 19.31, 24.85, 28.15, 36.12, 40.05, 42.09, 64.16, 66.07,
72.21, 76.52, 82.77, 108.13, 111.60, 126.45, 128.59, 128.75, 133.70,
138.76, 150.34, 156.50. Found: C, 77.11; H, 7.28; N, 7.38%. Calcd for
C25H28N2O2: C, 77.29; H, 7.26; N, 7.21%.
1
1245, 1155, 1108, 840, 811, 773, 653 cm−1; H NMR (500 MHz,
CDCl3) δ = 1.68 (2H, m), 1.84 (2H, m), 2.43 (2H, t, J = 6.8 Hz),
2.97 (6H, s), 4.22 (2H, t, J = 6.5 Hz), 6.59 (2H, d, J = 9.1 Hz), 6.80
(1H, br s), 7.34 (2H, d, J = 9.1 Hz), 7.51 (2H, d, J = 9.1 Hz), 7.55
(2H, d, J = 9.1 Hz); 13C NMR (125 MHz, CDCl3) δ = 19.32, 24.83,
27.96, 40.05, 65.03, 66.30, 72.16, 82.54, 108.02, 111.62, 118.02,
124.15 (q, JCF = 204 Hz), 125.15 (q, JCF = 25 Hz), 126.32 (q, JCF = 3
Hz), 133.73, 141.03, 150.40, 153.15, one of the acetylenic peaks
overlapped with a solvent peak. Found: C, 67.17; H, 5.52; N, 6.46%.
Calcd for C24H23F3N2O2: C, 67.28: H, 5.41: N, 6.54%.
8-[4-(N,N-Dimethylamino)phenyl]octa-5,7-diynyl N-(4-
Chlorophenyl)carbamate 5c. Yield 88%; mp 131 °C; IR (KBr)
3288, 2925, 2857, 2360, 1697, 1592, 1245, 823 cm−1; 1H NMR (500
MHz, CDCl3) δ = 1.68 (2H, m), 1.83 (2H, m), 2.43 (2H, t, J = 6.8
Hz), 2.98 (6H, s), 4.20 (2H, t, J = 6.3 Hz), 6.59 (2H, d, J = 8.8 Hz),
7.25−7.28 (4H, m), 7.33 (1H, br s), 7.34 (2H, d, J = 8.8 Hz); 13C
NMR (100 MHz, CDCl3) δ = 19.03, 24.52, 27.75, 39.81, 64.58,
66.00, 71.95, 82.39, 107,77, 111.38, 119.59, 128.44, 128.77, 133.50,
136.38, 150.13, 153.21, one of the acetylenic peaks overlapped with a
solvent peak. Found: C, 69.95; H, 5.87; N, 7.09%. Calcd for
C23H23N2O2: C, 69.92; H, 5.73; N, 7.04%.
8-[4-(N,N-Dimethylamino)phenyl]octa-5,7-diynyl N-(4-
Methoxyphenyl)carbamate 5d. Yield 69%; mp 105 °C; IR (KBr)
3316, 2965, 2938, 2235, 2130, 1702, 1606, 1536, 1415, 1363, 1243,
1180, 1074, 1025, 817, 781, 734, 634, 522 cm−1; 1H NMR (500 MHz,
CDCl3) δ = 1.66 (2H, m), 1.82 (2H, m), 2.41 (2H, t, J = 6.8 Hz),
2.97 (6H, s), 3.77 (3H, s), 4.18 (2H, t, J = 6.3 Hz), 6.54 (1H, br s),
6.59 (2H, d, J = 9.1 Hz), 6.85 (2H, d, J = 9.1 Hz), 7.28 (2H, br d),
7.34 (2H, d, J = 9.1 Hz); 13C NMR (125 MHz, CDCl3) δ = 19.31,
24.86, 28.06, 40.03, 55.45, 64.51, 66.15, 72.20, 76.59, 82.70, 108.11,
111.60, 114.20, 120.64, 130.91, 133.70, 150.35, 153.94, 155.90.
Found: C, 73.61; H, 7.03; N, 7.15%. Calcd for C24H26N2O3: C, 73.82;
H, 6.71; N, 7.17%.
8-[4-(N,N-Dimethylamino)phenyl]octa-5,7-diynyl N-Benzylcar-
bamate 5e. Yield 80%; mp 86 °C; IR (KBr) 3286, 3031, 2948,
2896, 2233, 2130, 1681, 1604, 1521, 1454, 1365, 1267, 1232, 1193,
1135, 1091, 1027, 944, 815, 750, 698, 530 cm−1; 1H NMR (500 MHz,
CDCl3) δ = 1.64 (2H, m), 1.77 (2H, m), 2.40 (2H, t, J = 6.8 Hz),
2.98 (6H, s), 4.13 (2H, t, J = 6.6 Hz), 4.37 (2H, d, J = 5.7 Hz), 4.96
(1H, br t), 6.59 (2H, d, J = 9.0 Hz), 7.26−7.31 (3H, m), 7.32−7.37
(4H, m); 13C NMR (125 MHz, CDCl3) δ = 19.29, 24.84, 28.07,
40.05, 45.00, 64.40, 66.08, 72.21, 76.53, 82.76, 108.11, 111.59, 127.42
(overlapping two peaks), 128.62, 133.70, 138.49, 150.33, 156.62.
Found: C, 76.85; H, 7.16; N, 7.52%. Calcd for C24H26N2O2: C, 76.98;
H, 7.00; N, 7.48%.
Melting points were determined by differential scanning calorim-
etry (DSC) using an SII DSC 6220 calorimeter with a heating rate of
5 °C min−1. FT-IR spectra were measured using a Horiba FT-720
1
spectrometer. H and 13C NMR spectra were recorded on a JEOL
JNM-ECX-400 or -500 instrument. Chemical shifts were calibrated by
1
TMS for H NMR and by CDCl3 (77 ppm) for 13C NMR. The
elemental analyses were performed with a PerkinElmer 2400 series II
CHNS/O elemental analyzer. UV−vis diffuse reflectance spectra were
measured using a JASCO V-570 spectrophotometer with an
integrated sphere (JASCO ILN-472).
X-ray single crystal analysis was performed using Rigaku Saturn 724
with a MoKα source. Data collection at 263 K, cell refinement, and
data reduction were performed using the CrystalClear-SM software.51
The structures were solved by the direct method using SHELXT52
and refined using SHELXL2014.53 All materials for publication were
prepared by Yadokari-XG 2009 software.54,55 Single crystals for the
analysis were prepared from the acetone−hexane solutions by the
slow evaporation method.
Solid-state polymerization was stimulated by irradiation of UV at
254 nm using a 16 W lamp (UVP R-52G). When the diffuse
reflectance spectra in the course of photopolymerization were
measured, UV was irradiated through the quartz window of the
holder of the samples, in which the monomers were mixed with
potassium bromide and ground. Conversions to the corresponding
polymers were obtained by the gravimetric method. The samples after
UV irradiation for 350 h were weighed (w0) and put into acetone to
be the dispersions with the concentration of 1 g/L. They were
sonicated for 10 min and stored for more than 12 h. Then, they were
filtered using membrane filters (Durapore 1.0 μm, VVHP). The
filtered materials were dried for 1 day and weighed (w). The
conversions were calculated by the following equation: 100w/w0 (%).
The ionization potentials of the monomers and the corresponding
polymers were examined using photoelectron yield spectroscopy
(PYS) in air obtained by a Riken Keiki AC-3 spectrometer. For the
monomer samples, the powdered crystals were pressed on glass
substrates, and the light intensity for the measurements was set to 10
nW. For the UV-irradiated samples, the samples on membrane filters,
C
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Table 1. Crystallographic Data of 5a−5f
compound
5a
5b
5c
5d
5e
5f
formula
C23H24N2O2
360.44
triclinic
C24H23F3N2O2
428.44
triclinic
C23H23ClN2O2
394.88
triclinic
C24H26N2O2
390.47
triclinic
C24H26N2O2
374.47
triclinic
C25H28N2O2
388.49
triclinic
formula weight
crystal system
space group
a/Å
b/Å
c/Å
α/deg
β/deg
γ/deg
V/Å
P1
̅
P1
̅
P1
̅
P1
̅
P1
̅
P1
̅
5.1870(14)
12.317(4)
15.634(5)
102.428(9)
95.580(11)
93.238(10)
967.7(5)
2
4.9855(2)
13.0325(5)
18.1787(8)
109.430(4)
91.960(4)
100.825(4)
1088.07(8)
2
5.159(3)
11.221(8)
18.366(11)
101.280(18)
95.30(3)
97.728(15)
1025.5(11)
2
10.0211(4)
18.6993(6)
23.8075(8)
75.710(3)
87.998(3)
83.592(3)
4296.1(3)
8
5.9428(3)
8.6694(5)
42.721(3)
88.9940(10)
89.4990(10)
75.168(6)
2127.3(2)
4
5.113(3)
12.199(6)
18.218(9)
74.023(11)
86.068(14)
85.288(15)
1087.5(10)
2
Z
Dx/Å3
R
1.237
0.0527
1.308
0.0458
1.279
0.0573
1.207
0.0556
1.169
0.0636
1.186
0.0522
wR2
0.1490
0.1446
0.1465
0.1656
0.1734
0.1502
GOF
1.046
1.027
1.098
1.027
1.066
1.036
which were obtained in the experiments to evaluate the conversions
mentioned above, were used, and the light intensity was 100 nW.
the monomer alignment in the crystals. For 5a, 5b, 5c, 5e, and
5f, the adjacent molecules have only the translation relation in
the crystals (Figure 5a−c and Figure 6a,b,d). Thus, the
polymerization direction must be along one of three
crystallographic axes. The shortest side lengths of their unit
cells are around 5 Å of the a axis, indicating that the a axis can
be the solid-state polymerization direction. For 5e, two
conformers form two monomer arrays, each of which is
composed of one conformer. Figure 6a,b show the monomer
arrays compose of conformer A (A1 and A2 in Figure 4e) and
conformer B (B1−B4 in Figure 4e). However, for 5d, two of
four conformers form one monomer array and the other two
form another monomer array along a axis. In each array,
different conformers alternately align (··ABAB·· or ··CDCD··
of conformers in Figure 4d), and one of the array is shown in
Figure 5d. Except for 5e, the monomer alignment motif
mentioned above is all based on intermolecular hydrogen
bonding of the urethane groups between adjacent molecules,
i.e., directions of the hydrogen bonding and the monomer
stacking array are the same. However, the monomer alignment
motif of 5e is different. Although there is intermolecular
hydrogen bonding of urethane groups between adjacent
molecules even in 5e along the b axis (Figure 6c), the different
conformers with opposite molecular directions are alternately
aligned and the butadiyne moieties are not stacked along this
direction. Thus, polymerization cannot progress along the b
axis, and the nearest stacking distance between the monomers
in the same orientation was found to be along the a axis.
Table 2 summarizes structural parameters and characteristics
in the crystals. As mentioned above, directions of intermo-
lecular hydrogen bonding and butadiyne stacking are the same
except for 5e. Thus, the following discussion is related for the
five compounds except 5e. When we pay attention to hydrogen
bonding along butadiyne stacking, distance between nitrogen
and oxygen atoms of adjacent urethane groups is from 2.88 to
3.03 Å, and the angle between O···H−N intermolecular
hydrogen bond and H−N covalent bond of urethane groups is
from 152.2° to 163.8°. These relatively small variations seem
to cause a basic motif of molecular stacking. As a result,
distance d becomes around 5 Å from 4.99 to 5.19 Å. Focusing
on the conformation of the butylene chain between butadiyne
and urethane groups, three compounds have all-trans
structures (ttt in Table 2), and two have gauche-trans-gauche
RESULTS AND DISCUSSION
■
Single crystals appropriated for X-ray crystallographic analysis
were obtained for all compounds in this study. Crystallo-
graphic data of monomers 5a−5f are shown in Table 1.
Monomer structures in the crystals are displayed in Figure 4.
̅
All crystals belongs to triclinic space group P1. However, the
number of molecules in a unit cell (Z) is different. Compounds
5a, 5b, 5c, and 5f have two molecules related by the center of
symmetry in a unit cell. Molecules of 5a showed disorder in
the butylene chain (A1 and A2 in Figure 4a), and their
occupancy factors were 0.865 and 0.135, respectively. For 5b,
rotation disorder was found in the trifluoromethyl group (A1
and A2 in Figure 4b), and their occupancy factors were 0.663
and 0.337, respectively. Monomer 5c has a single molecular
structure as shown in Figure 4c. For 5f, disorder was
recognized in the phenethyl group (A1 and A2 in Figure 4f),
and their occupancy factors were 0.510 and 0.490, respectively.
However, 5d and 5e were analyzed to have molecules with
different conformations. For 5d, four conformers A−D were
found as shown in Figure 4d. Structures of A and D are similar
and also those of B and C are similar. However, within each
pair, the details of the structures are different. Molecular
structures of 5e were much complicated. There are two
conformers A and B, and each conformer showed disorder. For
conformer A, disorder was observed in the benzyl group (A1
and A2 in Figure 4e), and their occupancy factors were 0.5
each. Meanwhile, conformer B has disorder around both
aromatic rings. The structures of B1 and B2 in Figure 4e are
shown with disorder in the benzyl group, and the DMAP
group is fixed to one structure. Occupancy factors of the benzyl
group in B1 and B2 were 0.5 each. In the structures of B1, B3,
and B4, the benzyl group is fixed, and disorder around the
DMAP group is shown. Occupancy factors of the DMAP
group for these structures were 0.34, 0.34, and 0.32,
respectively.
As mentioned above, monomer alignment is more important
from the point of view of the solid-state polymerization, and
adjacent monomer distance d should be around 5 Å. Thus, we
picked up monomer stacking arrays along one direction with d
of around 5 Å from the crystal structures. Figures 5 and 6 show
D
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 5. Monomer arrays in the crystals of N-phenylcarbamates: (a)
5a, (b) 5b, (c) 5c, and (d) 5d. Hydrogen atoms are omitted.
Intermolecular hydrogen bonds are indicated by red dashed lines.
Figure 6. Monomer arrays in the crystals of N-benzylcarbamates and
N-phenethylcarbamates: (a−c) 5e and (d) 5f. Hydrogen atoms are
omitted. Intermolecular hydrogen bonds are indicated by red dashed
lines.
Figure 4. Monomer structures in the crystals: (a) 5a, (b) 5b, (c) 5c,
(d) 5d, (e) 5e, and (f) 5f. In the symbols of the structures, alphabets
indicate conformers and numbers indicate disordered structures of the
conformers.
structures (gtg in Table 2). From the point of view of alkyl
chain packing, the latter structures are apt to be loose. Actually,
E
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Table 2. Structural Parameters and Characteristics of 5a−5f in Crystals
packing parameters
hydrogen-bonding parameters
a
a
b
c
compound
d /Å
θ /deg
ϕ /deg
O···N/Å
∠O···H−N/deg
conformation of butylene group
5a
5b
5c
5d
5.19
4.99
5.16
4.97, 5.07
5.03, 5.01
5.94
5.94
5.11
47.4
51.6
48.1
71.0, 70.5
71.3, 71.0
41.1
53.4, 55.7, 53.3
45.7
70.3
67.6
75.4
17.8, 79.4
89.2, 26.3
66.8
3.03
2.92
3.00
2.89, 2.88
2.91, 2.90
(2.87)
(2.82)
2.93
163.8
155.3
156.0
158.8, 164.1
153.6, 152.2
(178.0)
(156.1)
156.1
gtg
ttt
gtg
ttt, ttt
ttt, ttt
gtg
ttt
ttt
c
d
g
e
e
f
i
f
h
h
i
k
k
5e
5f
j
j
k
k
28.8, 47.4, 27.1
80.0
a
b
Geometric definitions of distance d and angle θ are shown in Figure 1. Geometric definition of angle ϕ is displayed in Figure 7. Methylene chain
conformation is expressed for three C−C bonds from the carbon attached to the butadiyne moiety to that next to the urethane group. Symbols g
d
and t indicate gauche and trans conformations, respectively. Average distances from conformer A to conformer B and from B to A, respectively, in
e
Figure 4d, in the direction from the carbon atom to the oxygen atom of the carbonyl group. For conformer A and for conformer B, respectively, in
f
g
Figure 4d. From conformer A to conformer B and from B to A, respectively, in Figure 4d. Average distances from conformer C to conformer D
h
and from D to C, respectively, in Figure 4d, in the direction from the carbon atom to the oxygen atom of the carbonyl group. For conformer C
and for conformer D, respectively, in Figure 4d. From conformer C to conformer D and from D to C, respectively, in Figure 4d. Angles for the
structures of B1, B3, and B4, respectively, in Figure 4e. Stacking direction of butadiyne moieties and direction of intermolecular hydrogen bonding
i
j
k
are not parallel.
the gtg structures showed longer d than the ttt structures, i.e., d
of no more than 5.11 Å for the ttt structures and that of more
than 5.16 Å for the gtg structures. Meanwhile, the range of
angle θ is spread, although four compounds of five showed θ of
around 45° from 45.7° to 51.6°. Large deviation of θ from 45°
was found in 5d, i.e., θ of about 71°. However, 5e, whose
intermolecular hydrogen bonding is not parallel to the
butadiyne stacking direction, showed longer d of 5.94 Å,
although θ is around 45°, i.e., 41.1° and 55.7°. According to
the criteria for the solid-state 1,4-addition polymerization of
butadiyne derivatives, i.e., d ≈ 5 Å and θ ≈ 45°, these results
suggested that 5a, 5b, 5c, and 5f would polymerize in the
regular 1,4-addition manner, while regular polymerization was
not expected for 5d with larger θ of about 70° and 5e with
longer d of about 5.9 Å. Angle ϕ in Table 2 indicates the angle
between the plane of the butadiyne stacking array and the π-
conjugated phenyl plane directly attached to the butadiyne
moiety (Figure 7). The former plane can be a π-conjugated
The other angle problem is related to the bond angle
changes at C1 and C4 in Figure 2c in the course of
polymerization, i.e., transformation of sp carbons with the
bond angle of 180° to sp2 carbons with the bond angle of 120°.
From the model structures of [4-(dimethylamino)phenyl]-
butadiyne moiety and the corresponding polymer, the atom
displacements (r) due to polymerization were calculated
(Supporting Information). Large r values were obtained for
the nitrogen and carbons in the dimethylamino group to be 1.9
Å and 2.2−2.4 Å, respectively. However, the r values for the
phenyl carbons ranged from 0.4−1.2 Å, which were
comparable to those of C1 and C4 of 1.1 Å. Thus, in order
to realize more efficient solid-state polymerization of phenyl-
butadiyne groups, introduction of intramolecular or inter-
molecular mechanisms to compensate relatively large displace-
ment of the substituents of the aromatic ring should be
considered, e.g., introduction of flexible or bulky substitu-
ents.56−59
Solid-state polymerization of the powder samples were
monitored by UV−vis diffuse reflectance spectra (Figure 8).
Six spectra in Figure 8 can be classified into two categories.
One is the spectra with characteristic absorption due to PDA
exciton and the spectra of 5a, 5b, 5c, and 5f belong to this
category. These absorption spectra indicate regular 1,4-
addition polymerization to form an ene-yne sequence of the
PDA structure since there are a lot of examples that regularly
polymerized PDAs display characteristic absorption bands in
the longer wavelength region than 500 nm, resulting in colors
from blue to red in general.56−58,60−67 The absorption maxima
of these spectra at the initial stage of polymerization were 637,
660, 672, and around 610 nm for 5a, 5b, 5c, and 5f,
respectively. As mentioned above, these four compounds were
found to have monomer stacks appropriate for solid-state
polymerization, and these structural features prove regular 1,4-
addition polymerization resulting in spectra with the excitonic
absorption. The other is spectra without absorption maxima in
the visible region and absorbance increased as the wavelength
became shorter from the absorption edge, e.g., 5d and 5e. The
data of crystallographic structures of 5d and 5e revealed that
these monomer arrays were not suitable for regular 1,4-
Figure 7. Dihedral angle ϕ between the phenyl ring plane and the
butadiyne-array plane, which is considered to become a π-conjugated
plane of PDA backbone after polymerization.
backbone plane after polymerization. Thus, if ϕ is small even
after polymerization, the conjugation effect from substituted
phenyl groups effectively transferred to the backbone. From
the geometric consideration based on d of 5 Å and the phenyl
ring thickness of 3.4 Å, the smallest ϕ is calculated to be
around 43°. However, 5a, 5b, 5c, and 5f showed much larger ϕ
angles from 67° to 80°. This may be due to steric hindrance
between dimethylamino groups. For 5d and 5e, smaller angles
than 43° were observed. In the case of 5d, conformers with
small ϕ of around 20° and large ϕ of near 90° are alternately
aligned. Meanwhile, large d can be small ϕ for 5e.
F
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 8. UV−visible diffuse reflectance spectra in the course of UV irradiation: (a) 5a, (b) 5b, (c) 5c, (d) 5d, (e) 5e, and (f) 5f.
addition and that these structural features reflected their
absorption spectra without characteristic excitonic bands.
Conversion from the monomers to the corresponding
polymers were obtained by the gravimetric method. Since
UV light irradiated was not able to fully penetrate the
pulverized samples, the absolute conversions were not high.
However, relative polymerizability can be discussed. For the
former class of compounds, conversions of 5a, 5b, 5c, and 5f
were 6%, 12%, 9%, and 16%, respectively. Conversions of 5d
and 5e in the latter class were ∼0% and 7%, respectively, and
5e was found to show relatively high conversion comparable to
5a and 5c. In order to clarify this reason, intermolecular C···C
distances relating to 1,4- and 1,2-addition polymerization were
investigated for all structures (Table 3). As was expected from
the discussion above, polymerization of 5a, 5b, 5c, and 5f were
again confirmed to be 1,4-addtion, i.e., C1···C4 distances of 5a,
5b, 5c, and 5f are 3.36−3.97 Å, which are shorter than the
corresponding C1···C2 and C3···C4 distances. However, C1···
C4 distances of 5d are longer than the corresponding C1···C2
and C3···C4 distances. This indicates that 1,2-addition of 5d is
easier than the regular 1,4-addition. For 5e, both conformer
arrays have smaller C1···C4 distances than the corresponding
C1···C2 and C3···C4 distances, and the C1···C4 distance
between two conformers of A is 3.97 Å, which is similar to that
of 5b. Accordingly, 5e can be polymerized in 1,4-addtion
manner, and the conversion may become relatively high.
However, d of 5.94 Å for 5e is much longer than 5 Å, and
regularity of the polymerization is low because of the large
structural mismatch between the monomer array and the
resulting polymer in the crystals.
The ionization potentials of the monomers and the
corresponding polymers were evaluated by PYS in air.
Among the six compounds, the monomer ionization potentials
of 5c, 5e, and 5f could be obtained to be 5.72, 5.68, and 5.66
eV, respectively. In our previous studies, we obtained the
ionization potentials of CP- and PC-type monomers (Figure 2)
to be about 6.0 and 5.8 eV, respectively.45,46 In comparison
with these values, DMAP-type monomers have smaller
ionization potentials, which agreed with the results on the
HOMO energy calculation mentioned in the Introduction.
G
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
molecular hydrogen bonding and the butadiyne stacking,
methylene chain conformation including gauche form, and
disorder of the aromatic rings at the molecular ends. Thus, if
we can suppress such structural variations by introducing
another molecular interactions, finer tuning for the crystal
structures having regularly polymerizable stacks seems to be
possible. In addition, introduction of intramolecular or
intermolecular mechanisms to compensate relatively large
displacement of the substituents of the aromatic ring seemed
to be considered for efficient conversion.
Table 3. Intermolecular Carbon Atom Distance Related to
Solid-State Addition Polymerization
b
intermolecular carbon atom distance /Å
a
c
d
d
compound
structure
C1···C4
C1···C2
C3···C4
5a
5b
5c
5d
3.825
3.966
3.856
5.100
5.272
5.247
5.184
3.973
4.771
3.664
4.467
4.350
4.454
4.644
4.802
4.763
4.734
5.086
5.289
4.354
4.468
4.336
4.449
4.741
4.849
4.805
4.751
5.120
5.450
4.365
A···B
B···A
C···D
D···C
A···A
B1···B1
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.8b00815.
■
5e
5f
S
a
Molecular structures in the crystals are shown in Figure 4, and their
Estimation of atom displacements due to polymerization
(PDF)
b
alignments are displayed in Figures 5 and 6. Carbon numbering is
shown in Figure 2c. Bond formation between these two carbons
results in 1,4-addition polymerization. Bond formation between
c
d
Accession Codes
these two carbons results in 1,2-addition polymerization.
CCDC 1844165−1844170 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
The ionization potentials of the photopolymerized samples
could be obtained for 5c and 5f, and they were 5.92 and 6.12
eV, respectively. These values were quite unexpected because
the ionization potentials of PDAs usually decrease compared
with the corresponding monomers because of the HOMO
energy elevation caused by π-conjugation extension. The
reason is not clear, but one of the plausible explanations is as
follows: Generally, the dimethylamino group is less stable than
the carbazolyl group, and the side reactions other than
polymerization, such as photooxidation,68,69 may occur during
UV irradiation at the outermost surface of the samples. These
side reactions may lower the HOMO energy levels to increase
the ionization potentials.
AUTHOR INFORMATION
Corresponding Author
*E-mail: okadas@yz.yamagata-u.ac.jp.
■
ORCID
Hiroshi Katagiri: 0000-0003-4100-9995
Shuji Okada: 0000-0001-9519-6648
Notes
The authors declare no competing financial interest.
CONCLUSION
■
ACKNOWLEDGMENTS
■
Six urethane derivatives with a DMAP-substituted butadiyne
moiety were synthesized, and their crystal structures and solid-
state polymerization behaviors were studied. Five of six
compounds 5a, 5b, 5c, 5d, and 5f showed the packing motif
that the direction of the intermolecular hydrogen bonding
between urethane groups and that of the butadiyne stacking
were parallel, and d was around 5 Å. When the butylene chain
conformation is gtg, d becomes longer compared with the ttt
conformation. Among them, four compounds except 5d
showed excitonic absorption after UV-induced polymerization,
indicating that the regular 1,4-addition polymerization
progressed to form PDAs. In the case of 5d, θ was much
larger than 45°, and the conversion to the polymer was quite
low. For 5e, the packing motif was not like the other five
compounds, and d was much larger than 5 Å. However, the
intermolecular carbon distance for 1,4-addition polymerization
was short enough, and the conversion to the polymer was
comparable to that of the compounds showing excitonic
absorption during polymerization, although polymerization of
5e was not so regular.
We thank Mr. Shinji Ishii and Mr. Shota Kaneko for their
contribution in the synthetic experiments. We also thank Prof.
Junji Kido, Prof. Yong-Jin Pu, and Prof. Hisahiro Sasabe for
cooperation on calculations using the Gaussian 09 program.
REFERENCES
■
(1) Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G.; Chiang, C. K.;
Heeger, A. J. Synthesis of Electrically Conducting Organic Polymers:
Halogen Derivatives of Polyacetylene, (CH)x. J. Chem. Soc., Chem.
Commun. 1977, 578−580.
(2) Pron, A.; Rannou, P. Processible Conjugated Polymers: From
Organic Semiconductors to Organic Metals and Superconductors.
Prog. Polym. Sci. 2002, 27, 135−190.
(3) Osaka, I.; McCullough, R. D. Advances in Molecular Design and
Synthesis of Regioregular Polythiophenes. Acc. Chem. Res. 2008, 41,
1202−1214.
̀
(4) Sauteret, C.; Hermann, J.-P.; Frey, R.; Pradere, F.; Ducuing, J.;
Baughman, R. H.; Chance, R. R. Optical Nonlinearities in One-
Dimensional-Conjugated Polymer Crystals. Phys. Rev. Lett. 1976, 36,
956−959.
(5) Yamamoto, T.; Yamada, W.; Takagi, M.; Kizu, K.; Maruyama,
T.; Ooba, N.; Tomaru, S.; Kurihara, T.; Kaino, T.; Kubota, K. π-
Conjugated Soluble Poly(aryleneethynylene) Type Polymers. Prep-
aration by Palladium-Catalyzed Coupling Reaction, Nonlinear Optical
Properties, Doping, and Chemical Reactivity. Macromolecules 1994,
27, 6620−6626.
As we have been demonstrated, introduction of intermo-
lecular hydrogen bonding to the arylbutadiyne monomers
generally increases probability of the solid-state polymer-
ization. In the present study, this empirical rule was
crystallographically confirmed. Partial structures, which caused
variation from the suitable condition for 1,4-addition polymer-
ization, were the directional mismatch between the inter-
(6) Hegde, P. K.; Adhikari, A. V.; Manjunatha, M. G.; Poornesh, P.;
Umesh, G. Third-Order Nonlinear Optical Susceptibilities of New
H
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Copolymers Containing Alternate 3,4-Dialkoxythiophene and (1,3,4-
Oxadiazolyl)pyridine Moieties. Opt. Mater. 2009, 31, 1000−1006.
(7) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.;
Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Light-Emitting
Diodes Based on Conjugated Polymers. Nature 1990, 347, 539−541.
(8) Kraft, A.; Grimsdale, A. C.; Holmes, A. B. Electroluminescent
Conjugated Polymers−Seeing Polymers in a New Light. Angew.
Chem., Int. Ed. 1998, 37, 402−428.
(9) Zhang, X.; Kale, D. M.; Jenekhe, S. A. Electroluminescence of
Multicomponent Conjugated Polymers. 2. Photophysics and
Enhancement of Electroluminescence from Blends of Polyquinolines.
Macromolecules 2002, 35, 382−393.
(10) Fuchigami, H.; Tsumura, A.; Koezuka, H. Polythienyleneviny-
lene Thin-Film Transistor with High Carrier Mobility. Appl. Phys.
Lett. 1993, 63, 1372−1374.
(11) Hamilton, M. C.; Kanicki, J. Organic Polymer Thin-Film
Transistor Photosensors. IEEE J. Sel. Top. Quantum Electron. 2004, 10,
840−848.
(12) Lee, J.; Han, A.-R.; Kim, J.; Kim, Y.; Oh, J. H.; Yang, C.
Solution-Processable Ambipolar Diketopyrrolopyrrole−Selenophene
Polymer with Unprecedentedly High Hole and Electron Mobilities. J.
Am. Chem. Soc. 2012, 134, 20713−20721.
(13) Kumaki, D.; Fujisaki, Y.; Tokito, S. Reduced Contact
Resistance and Highly Stable Operation in Polymer Thin-Film
Transistor with Aqueous MoOx Solution Contact Treatment. Org.
Electron. 2013, 14, 475−478.
(26) Tieke, B. Solid State Polymerization of Butadienes. Polymer-
ization of Long Chain Derivatives of Sorbic and Muconic Acid.
Colloid Polym. Sci. 1985, 263, 965−972.
(27) Tieke, B.; Chapuis, G. Solid State Polymerization of Butadienes
in Layer Structures. Mol. Cryst. Liq. Cryst. 1986, 137, 101−116.
(28) Matsumoto, A.; Matsumura, T.; Aoki, S. Stereospecific
Polymerisation of Diethyl (Z,Z)-Hexa-2,4-dienedioate in the Crystal-
line State. J. Chem. Soc., Chem. Commun. 1994, 1389−1390.
(29) Matsumoto, A.; Tanaka, T.; Tsubouchi, T.; Tashiro, K.;
Saragai, S.; Nakamoto, S. Crystal Engineering for Topochemical
Polymerization of Muconic Esters Using Halogen-Halogen and CH/π
Interactions as Weak Intermolecular Interactions. J. Am. Chem. Soc.
2002, 124, 8891−8902.
(30) Matsumoto, A. Reactions of 1,3-Diene Compounds in the
Crystalline State. Top. Curr. Chem. 2005, 254, 263−305.
(31) Hoang, T.; Lauher, J. W.; Fowler, F. W. The Topochemical 1,6-
Polymerization of a Triene. J. Am. Chem. Soc. 2002, 124, 10656−
10657.
(32) Xiao, J.; Yang, M.; Lauher, J. W.; Fowler, F. W. A
Supramolecular Solution to a Long-Standing Problem: The 1,6-
Polymerization of a Triacetylene. Angew. Chem., Int. Ed. 2000, 39,
2132−2135.
(33) Itoh, T.; Nomura, S.; Uno, T.; Kubo, M.; Sada, K.; Miyata, M.
Topochemical Polymerization of 7,7,8,8-Tetrakis(methoxycarbonyl)-
quinodimethane. Angew. Chem., Int. Ed. 2002, 41, 4306−4309.
(34) Itoh, T. Solution and Solid-State Polymerizations of Substituted
p-Quinodimethanes and p-Quinone Methides. Polymer 2005, 46,
6998−7017.
(35) Itoh, T.; Suzuki, T.; Uno, T.; Kubo, M.; Tohnai, N.; Miyata, M.
cis-Specific Topochemical Polymerization: Alternating Copolymeriza-
tion of 7,7,8,8-Tetrakis(methoxycarbonyl)quinodimethane with
7,7,8,8-Tetracyanoquinodimethane in the Solid State. Angew. Chem.,
Int. Ed. 2011, 50, 2253−2256.
(14) Sariciftci, N. S.; Braun, D.; Zhang, C.; Srdanov, V. I.; Heeger, A.
J.; Stucky, G.; Wudl, F. Semiconducting Polymer-Buckminsterfuller-
ene Heterojunctions: Diodes, Photodiodes, and Photovoltaic Cells.
Appl. Phys. Lett. 1993, 62, 585−587.
(15) Gunes, S.; Neugebauer, H.; Sariciftci, N. S. Conjugated
̈
Polymer-Based Organic Solar Cells. Chem. Rev. 2007, 107, 1324−
1338.
(36) Baughman, R. H.; Yee, K. C. Solid-State Polymerization of
Linear and Cyclic Acetylenes. Macromol. Rev. 1978, 13, 219−239.
(37) Enkelmann, V. Structural Aspects of the Topochemical
Polymerization of Diacetylenes. In Polydiacetylenes: Adv. Polym. Sci.;
Cantow, H.-J, Ed.; Springer-Verlag: Berlin, 1984; Vol. 63, pp 91−136.
(38) Nakanishi, H.; Matsuda, H.; Okada, S.; Kato, M. Preparation
and Nonlinear Optical Properties of Novel Polydiacetylenes. In
Frontiers of Macromolecular Science; Saegusa, T., Higashimura, T., Abe,
A., Eds.; Blackwell Scientific Publication: Oxford, 1989; pp 469−474.
(39) Sarkar, A.; Okada, S.; Matsuzawa, H.; Matsuda, H.; Nakanishi,
H. Novel Polydiacetylenes for Optical Materials: Beyond the
Conventional Polydiacetylenes. J. Mater. Chem. 2000, 10, 819−828.
(40) Patel, G. N.; Khanna, Y. P.; Ivory, D. M.; Sowa, J. M.; Chance,
R. R. Polymer Conversions in the γ-Ray Polymerization of Urethane-
Substituted Diacetylenes. J. Polym. Sci., Polym. Phys. Ed. 1979, 17,
899−903.
(41) Tachibana, H.; Kumai, R.; Hosaka, N.; Tokura, Y. Crystal
Structures, Polymerization, and Thermochromic Phase Changes in
Urethane-Substituted Diacetylenes Crystals with Varying Alkyl Chain
Lengths. Chem. Mater. 2001, 13, 155−158.
(42) Kim, W. H.; Kodali, N. B.; Kumar, J.; Tripathy, S. K. A Novel,
Soluble Poly(diacetylene) Containing an Aromatic Substituent.
Macromolecules 1994, 27, 1819−1824.
(43) Sarkar, A.; Okada, S.; Nakanishi, H.; Matsuda, H.
Polydiacetylenes from Asymmetrically Substituted Diacetylenes
Containing Heteroaryl Side Groups for Third-Order Nonlinear
Optical Properties. Macromolecules 1998, 31, 9174−9180.
(44) Shibuya, T.; Tatewaki, Y.; Okada, S. Synthesis of Poly-
diacetylenes with Pyridyl Groups Directly Bound to the Main Chain.
Mol. Cryst. Liq. Cryst. 2012, 568, 93−97.
(45) Ikeshima, M.; Mamada, M.; Katagiri, H.; Minami, T.; Okada,
S.; Tokito, S. Synthesis and Solid-State Polymerization of Diacetylene
Derivatives with an N-Carbazolylphenyl Group. Bull. Chem. Soc. Jpn.
2015, 88, 843−849.
(46) Ikeshima, M.; Mamada, M.; Minami, T.; Tokito, S.; Okada, S.
Synthesis and Solid-State Polymerization of Diacetylene Derivatives
(16) Facchetti, A. π-Conjugated Polymers for Organic Electronics
and Photovoltaic Cell Applications. Chem. Mater. 2011, 23, 733−758.
(17) Adegoke, O. O.; Jung, I. H.; Orr, M.; Yu, L.; Goodson, T., III
Effect of Acceptor Strength on Optical and Electronic Properties in
Conjugated Polymers for Solar Applications. J. Am. Chem. Soc. 2015,
137, 5759−5769.
(18) Wegner, G. Topochemische Reaktionen von Monomeren mit
konjugierten Dreifachbindungen I. Mitt.: Polymerisation von
Derivaten des 2.4-Hexadiin-1.6-diols im kristallinen Zustand. Z.
Naturforsch., B: J. Chem. Sci. 1969, 24B, 824−832.
(19) Hasegawa, M.; Suzuki, Y. Four-Center Type Photopolymeriza-
tion in the Solid State: Poly-2,5-distrylpyrazine. J. Polym. Sci., Part B:
Polym. Lett. 1967, 5, 813−815.
(20) Hasegawa, M.; Hashimoto, Y. Kaleidoscopic Photochemical
Behavior of Unsymmetric Diolefin Crystals. Mol. Cryst. Liq. Cryst. Sci.
Technol., Sect. A 1992, 219, 1−15.
(21) Hasegawa, M. Photodimerization and Photopolymerization of
Diolefin Crystals. Adv. Phys. Org. Chem. 1995, 30, 117−171.
(22) Garai, M.; Santra, R.; Biradha, K. Tunable Plastic Films of a
Crystalline Polymer by Single-Crystal-to-Single-Crystal Photopolyme-
rization of a Diene: Self-Templating and Shock-Absorbing Two-
Dimensional Hydrogen-Bonding Layers. Angew. Chem., Int. Ed. 2013,
52, 5548−5551.
(23) Mandal, R.; Garai, M.; Biradha, K. Hydrogen-bonded Two-fold
Interpenetrated Diamondoid Networks for Solid-State [2 + 2]
Polymerizations of Criss-crossed Olefins: Molecular Connections vs
Supramolecular Connections. Cryst. Growth Des. 2017, 17, 5061−
5064.
(24) Garai, M.; Biradha, K. Water-Resistant and Transparent Plastic
Films from Functionalizable Organic Polymers: Coordination
Polymers as Templates for Solid-State [2 + 2]-Photopolymerization.
Chem. - Eur. J. 2017, 23, 273−277.
(25) Tieke, B.; Wegner, G. Solid-State Polymerization of 1,4-
Disubstituted trans,trans-Butadienes in Perovskite-Type Layer Struc-
tures. Makromol. Chem., Rapid Commun. 1981, 2, 543−549.
I
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Directly Substituted by a Phenylcarbazole Moiety. Polym. J. 2016, 48,
1013−1018.
carbazolyl)-2,4-hexadiyne]. Chem. Phys. Lett. 1978, 54, 295−299.
(b) Apgar, P. A.; Yee, K. C. Poly[1,6-di(N-carbazolyl)-2,4-hexadiyne].
Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1978, 34,
957−959.
(47) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.;
Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.;
Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.;
Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J.
C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, J.; Millam, M.; Klene,
M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.;
Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.;
Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.;
Cioslowski, J.; Fox, D. J. Gaussian 09, revision D.01; Gaussian,
Wallingford, CT, 2013.
(62) (a) Chance, R. R.; Patel, G. N.; Witt, J. D. Thermal effects on
the optical properties of single crystals and solution-cast films of
urethane substituted polydiacetylenes. J. Chem. Phys. 1979, 71, 206−
́
211. (b) Brouty, C.; Spinat, P.; Whuler, A. Determination Structurale
́
du Poly{bis[(butoxycarbonylmethylcarbamoyloxy)-4 butyl]-1,2 bu-
̀
̀
tene-1 yne-3 ylene} [poly(4BCMU)] par Minimisation des Energies
d’Interactions Moleculaires. Acta Crystallogr., Sect. C: Cryst. Struct.
́
Commun. 1988, 44, 1070−1076.
(63) (a) Enkelmann, V.; Schleier, G. Poly[1,2-bis-
(diphenylaminomethyl)-l-buten-3-ynylene]. Acta Crystallogr., Sect. B:
Struct. Crystallogr. Cryst. Chem. 1980, 36, 1954−1956. (b) Morrow,
M. E.; White, K. M.; Eckhardt, C. J.; Sandman, D. J. Single-Crystal
Reflection and Raman Spectra of the Polydiacetylene THD. Chem.
Phys. Lett. 1987, 140, 263−269.
(64) (a) Wenz, G.; Wegner, G. Molecular Weight Distribution and
Solution Properties of a Poly(diacetylene). Makromol. Chem., Rapid
Commun. 1982, 3, 231−237. (b) Wenz, G.; Muller, M. A.; Schmidt,
̈
M.; Wegner, G. Structure of Poly(diacetylenes) in Solution.
Macromolecules 1984, 17, 837−850.
(48) Okada, S.; Matsuda, H.; Otsuka, M.; Nakanishi, H.; Kato, M.
Synthesis and Solid-State Polymerization of ω-(4-Aryl-1,3-butadiynyl)
Substituted 1-Alkanol and Alkanoic Acid. Bull. Chem. Soc. Jpn. 1994,
67, 483−489.
(49) Ishii, S.; Kaneko, S.; Tatewaki, Y.; Okada, S. Synthesis and
Solid-State Polymerization of 4-(Dimethylamino)phenylbutadiyne
Derivatives and Their Charge-Transfer Complexes. Mol. Cryst. Liq.
Cryst. 2013, 580, 64−68.
(50) Okada, S.; Matsuda, H.; Masaki, A.; Nakanishi, H.; Hayamizu,
K. Novel Linear and Ladder Polymers from Tetraynes for Nonlinear
Optics. Proc. SPIE 1991, 25−34.
(51) CrystalClear, Rigaku Corporation, Tokyo, Japan, 2008.
(52) Sheldrick, G. M. Program for the Solution of Crystal Structures.
Acta Crystallogr., Sect. A: Found. Adv. 2015, 71, 3−8.
(53) Sheldrick, G. M. Program for the Refinement of Crystal
Structures. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3−8.
(54) Wakita, K. Yadokari-XG, Software for Crystal Structure
Analyses, 2001.
(55) Kabuto, C.; Akine, S.; Nemoto, T.; Kwon, E. Release of
Software (Yadokari-XG 2009) for Crystal Structure Analyses. Nippon
Kessho Gakkaishi 2009, 51, 218−224.
(65) Okada, S.; Hayamizu, K.; Matsuda, H.; Masaki, A.; Nakanishi,
H. Structures of the Polymers Obtained by the Solid-State
Polymerization of Diyne, Triyne, and Tetrayne with Long Alkyl
Substituents. Bull. Chem. Soc. Jpn. 1991, 64, 857−863.
(66) (a) Sandstedt, C. A.; Eckhardt, C. J.; Downey, M. J.; Sandman,
D. J. Optical, Calorimetric, and Mass Spectroscopic Study of
Nonthermochromic Crystalline Forms of the Polydiacetylene Bis-
(ethylurethane)-5,7-Dodecadiyne-1,12-diol (ETCD). Chem. Mater.
1994, 6, 1346−1350. (b) Wang, X.; Sandman, D. J.; Enkelmann, V.;
Chen, C.-H.; Foxman, B. M. Crystal and Molecular Structure of the
bis-Ethyl Urethane of 5,7-Dodecadiyn-1,12,diol (ETCD). J. Macromol.
Sci., Part A: Pure Appl.Chem. 2008, 45, 914−916.
(67) Pigos, J. M.; Zhu, Z.; Musfeldt, J. L. Optical Properties of a
Supramolecular Assembly Containing Polydiacetylene. Chem. Mater.
1999, 11, 3275−3278.
(68) Galindo, C.; Jacques, P.; Kalt, A. Photodegradation of the
Aminoazobenzene Acid Orange 52 by Three Advanced Oxidation
Processes: UV/H2O2, UV/TiO2 and VIS/TiO2: Comparative
Mechanistic and Kinetic Investigations. J. Photochem. Photobiol., A
2000, 130, 35−47.
(56) (a) Wegner, G. Topochemical Polymerization of Monomers
with Conjugated Triple Bonds. Makromol. Chem. 1972, 154, 35−48.
(b) Nakanishi, H.; Matsuda, H.; Kato, M.; Theocharis, C. R.; Jones,
W. Single-Crystal Study of the Solid-State Polymerisation of
Butadiynylenebis-(m-acetamidobenzene). J. Chem. Soc., Perkin Trans.
2 1986, 1965−1967.
(69) Al-Nu’airat, J.; Altarawneh, M.; Gao, X.; Westmoreland, P. R.;
Dlugogorski, B. Z. Reaction of Aniline with Singlet Oxygen (O2 1Δg).
J. Phys. Chem. A 2017, 121, 3199−3206.
(57) (a) Tokura, Y.; Koda, T.; Itsubo, A.; Miyabayashi, M.; Okuhara,
K.; Ueda, A. Optical Spectra in Polydiacetylene Crystals Substituted
with Fluorobenzenes. J. Chem. Phys. 1986, 85, 99−104. (b) Nakanishi,
H.; Matsuda, H.; Okada, S.; Kato, M. Nonlinear Optical Properties of
Polydiacetylenes with Conjugation between the Main Chain and the
Substituents. In Nonlinear Optics of Organics and Semiconductors:
Springer Proc. Phys.; Kobayashi, T., Ed.; Springer-Verlag: Berlin, 1989;
Vol. 36, pp 155−162.
(58) Okada, S.; Ohsugi, M.; Masaki, A.; Matsuda, H.; Takaragi, S.;
Nakanishi, H. Prearation and Nonlinear Optical Property of
Polydiacetylenes from Unsymmetrical Diphenylbutadiynes with
Trifluoromethyl Substituents. Mol. Cryst. Liq. Cryst. 1990, 183, 81−
90.
(59) Sato, H.; Okada, S.; Kimura, T.; Shimada, S.; Matsuda, H.;
Nakanishi, H. Synthesis of Pyridylbutadiyne Derivatives and Improve-
ment of Their Solid-State Polymerizability by Complexation with
Alkanoic Acid. Chem. Lett. 2006, 35, 412−413.
(60) Bloor, D.; Koski, L.; Stevens, G. C.; Preston, F. H.; Ando, D. J.
Solid State Polymerization of Bis-(p-toluene sulphonate) of 2,4-
Hexadiyne-1,6-diol. Part 1 X-ray Diffraction and Spectroscopic
Observations. J. Mater. Sci. 1975, 10, 1678−1688.
(61) (a) Hood, R. J.; Muller, H.; Eckhardt, C. J.; Chance, R. R.; Yee,
̈
K. C. Optical Properties of a Polydiacetylene Crystal: Poly-[1,6-di(N-
J
DOI: 10.1021/acs.cgd.8b00815
Cryst. Growth Des. XXXX, XXX, XXX−XXX