Synthesis and solid-state polymerization of 5-(pyren-1-yl)penta-2,4- diyn-1-ol derivatives with an n-phenylurethane or n-benzylurethane group

Shuhei Oshimizu, Shoko Takeshi, Tsubasa Sato, Ryohei Yamakado, Yoko Tatewaki, and Shuji Okada*

Article

Synthesis and Solid-State Polymerization of 5‑(Pyren-1-yl)penta-2,4-

diyn-1-ol Derivatives with an N‑Phenylurethane or

N ‑Benzylurethane Group

Cite This: https://dx.doi.org/10.1021/acs.cgd.0c00438

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ABSTRACT: A series of 5-(pyren-1-yl)penta-2,4-diyn-1-yl N-phenylcarbamates and

N-benzylcarbamates were synthesized. Phenyl groups in the N-phenyl and N-benzyl

moieties were unsubstituted (H-0 and H-1, respectively) and 3,4,5-trialkoxy

substituted (C O-0 and C O-1, respectively), in which the alkyl groups introduced

were methyl (m = 1), octyl (m = 8), dodecyl (m = 12), and hexadecyl (m = 16)

groups. Upon UV irradiation, a regular 1,4-addition polymerization to form

polydiacetylene was conﬁrmed for H-0, H-1, C O-1, C O-1, and C O-1. For

C O-0 and C O-1, the crystal structures were solved, and the reasons the regular

polymerization did not occur were clariﬁed. From the powder X-ray diﬀraction study,

crystallinities of C O-1 were found to be lower than those of C O-0, although C O-1

regularly polymerized. This indicates that the total crystallinity is not directly related to local ordering around one-dimensional arrays

for the polymerization direction. Polymerized C O-1 species were soluble in chloroform. Their processability enabled us to fabricate

cast ﬁlms of polydiacetylene as well as the monomer. The conductivities of C O-1 and the polymer (PC O-1) were evaluated in

the pristine and iodine-doped states and in the charge-transfer-complexed states with 2,3,5,6-tetraﬂuoro-7,7,8,8-tetracyanoquinodi-

methane. A conductivity of 1.2 × 10⁻S m for iodine-doped PC O-1 was achieved. In this case, pyrene moieties seemed to play

−1

an important role in realizing the appropriate electron transfer from pyrene moieties to iodine molecules and eﬀective π conjugation

between the pyrene moieties and the PDA backbone promoting charge transport.

INTRODUCTION

■

A variety of π-conjugated polymers have been investigated as

−3

4−6

materials for nonlinear optics,

electric conduction,

−9

10−12

13−16

electrochromism,

transistors,

light emission,

photovoltaics,

7−19

20−22

sensors,

etc., and many of them have

generally been synthesized via solution polymerization.

However, polydiacetylene (PDA) is an exception. It is

synthesized by the solid-state 1,4-addition polymerization of

butadiyne monomers. Since polymerization progresses top-

ochemically, the resulting polymers can have quite regular

stereostructures with high molecular weight. Although this is a

kind of ideal polymerization, it also has challenges. First, the

butadiyne monomers synthesized do not polymerize with a

high probability because of narrow acceptable conditions for

the solid-state polymerization. The monomers should satisfy

the following conditions to react via regular 1,4-addition

polymerization: the distance d between the adjacent

monomers in the array with the translation relation is

approximately 0.5 nm and angle θ between the translation

axis and the butadiyne rod in the monomer is approximately

Figure 1. Topochemical polymerization scheme of butadiyne

derivatives. Appropriate conditions for the regular 1,4-addition

polymerization are a distance d of approximately 0.5 nm and an

angle θ of approximately 45°.

Received: March 31, 2020

Revised: August 4, 2020

Published: August 5, 2020

24,25

5°, as shown in Figure 1.

Second, the polymers obtained

are generally insoluble and the processability is poor. However,

since PDA has a π-conjugated backbone, a wide range of

electronic and optical applications have been considered in

general. Thus, the molecular design and the related properties

XXXX American Chemical Society

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 2. Synthesis scheme of pyrenylbutadiyne derivatives with an N-phenylurethane or N-benzylurethane moiety.

have been extensively investigated. The properties investigated

are, for example, third-order nonlinear optical proper-

RESULTS AND DISCUSSION

■

Ten pyrenylbutadiyne derivatives with an N-phenylurethane or

N-benzylurethane moiety were synthesized according to Figure

2. From 1-bromopyrene (1), 1-ethynylpyrene (3) was

prepared via 2 as a product of Sonogashira coupling followed

by acetone elimination using potassium hydroxide. A Cadiot−

Chodkiewicz coupling reaction between 3 and 3-bromoprop-2-

yn-1-ol aﬀorded 5-(pyren-1-yl)penta-2,4-diyn-1-ol (4). Finally,

addition reaction of isocyanates to 4 gave the desired

compounds.

First, photopolymerization behaviors of the solid samples

were investigated using visible diﬀuse reﬂectance spectra (see

the Experimental Section for the sample preparation). Figure 3

shows the spectra obtained by UV irradiation of 254 nm. All

pyrenylbutadiyne derivatives showed an absorption increase in

the visible region, suggesting that polymerization occurred to

form extended π-conjugated structures. The spectral patterns

are roughly classiﬁed into two categories. Compounds in the

ﬁrst category (type I) showed spectra having absorption

maxima in the wavelength range between 550 and 700 nm after

,26−31

32−37

38−41

ties,

conductivities,

colorimetric properties,

etc.

From the viewpoint of the molecular design of PDA, PDAs

with π conjugation between the backbone and substituents are

interesting because of their improved electronic and optical

properties. However, the probability of solid-state polymer-

ization of butadiyne monomers directly substituted by

aromatic rings is lower than that of the monomers substituted

by alkyl groups in general. Thus, strategies to align the

monomers in polymerizable stacks are required. One of the

43,44

strategies is to use a supramolecular host−guest system.

The other is modiﬁcation by speciﬁc groups, which tend to

align monomers in one-dimensional (1D) arrays. We have

used the latter strategy to prepare butadiyne monomers with π

45,46

conjugation between the backbone and substituents.

For

example, butadiyne derivatives directly bound to electron-

7,48

49,50

donating aromatics such as pyrene,

aniline,

N-phenylcarbazole,

1,52

UV irradiation. Compounds of type I are H-0, H-1, C O-1,

and tetrathiaﬂuvalene (TTF) were recently

C O-1, and C O-1, whose absorption maxima at the longest

synthesized, and some of them polymerized regularly to form

PDAs with conjugated donors. Meanwhile, in order to improve

the PDA processability, one of the potential approaches is its

solubilization. Although some butadiyne derivatives with

urethane groups have been found to dissolve in organic

wavelengths were 646, 691, 668, 659, and 667 nm, respectively.

These absorption bands are generally assigned to an excitonic

absorption with its phonon sidebands originating from the

regularly polymerized PDA structure. Other compounds in the

second category (type II) showed an absorption increase in the

visible region upon UV irradiation but no absorption maxima

were observed in this region. In this case, the polymerization

scheme seems to be not as regular as for the compounds of

type I. Actually, in our previous study, we conﬁrmed by single-

crystal X-ray crystallographic analysis that the butadiyne

derivatives showing the polymer absorption of type II aligned

under the conditions with a large deviation from d = 0.5 nm

4,55

solvent,

we prepared those with 3,4,5-trialkoxyphenyl

(

TAOP) groups to impart self-organizing properties and

56,57

solubilities of their polymers.

In the present study, we focused on the preparation of

soluble PDAs with donor substituents directly bound to the π-

conjugated backbone. As a donor, we selected pyrene because

of its relatively high photostability, and TAOP groups were

introduced for solubilization. The alkyl chains in the TAOP

groups were varied among octyloxy, dodecyloxy, and

hexadecyloxy groups. For comparison, the derivatives with a

simple phenyl group instead of the TAOP group or with the

TAOP group containing methoxy groups were also synthe-

sized. The photopolymerizability and crystallinity of the

monomers and processability of the polymers were inves-

tigated. The electrical conductivities of the ﬁlms of a monomer

and the corresponding polymer were evaluated.

and θ = 45° in Figure 1.

Powder X-ray diﬀraction patterns of the monomers were

obtained as shown in Figure 4. Sharp diﬀraction peaks were

observed for the compounds with phenyl or trimethoxyphenyl

groups: i.e., H-0, H-1, C O-0, and C O-1. Among these

compounds, single crystals of C O-0 and C O-1 with large

enough sizes for X-ray crystallography were obtained and

analyzed. The crystal structures of C O-0 and C O-1 are

shown in Figures 5 and 6, respectively, and their crystallo-

graphic data are summarized in Table 1. C O-0 molecules

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 4. Powder X-ray diﬀraction patterns of (a) H-0, (b) H-1, (c)

C O-0, (d) C O-1, (e) C O-0, (f) C O-1, (g) C O-0, (h) C O-1,

(

i) C O-0, and (j) C O-1. One scale of the vertical axis corresponds

16 16

to 1 (=log 10), and the lowermost scale is 2 (=log 10 ) for each curve,

which is shifted by 2 to avoid overlap. Red asterisks on the peak tops

of the diﬀractograms (e)−(j) indicate that these peaks were used to

calculate the interlayer spacings.

of C O-1 does not form a hydrogen bond. This fact is also

supported by the IR spectral data. Almost all urethane

compounds in this study showed an absorption peak

corresponding to a CO stretching vibration in the range

−

of 1693−1697 cm , suggesting intermolecular hydrogen

bonding of the urethane groups. However, C O-1 exception-

−1

ally exhibited the peak at a higher wavenumber of 1722 cm ,

indicating an isolated CO bond without hydrogen bonding.

Figure 3. Visible diﬀuse reﬂectance spectra of (a) H-0, (b) H-1, (c)

C O-0, (d) C O-1, (e) C O-0, (f) C O-1, (g) C O-0, (h) C O-1,

As shown in Figure 6b, pyrene and butadiyne moieties of C O-

(

i) C O-0, and (j) C O-1 in the course of UV irradiation at 254 nm.

1 are alternately piled up. Thus, a regular 1,4-addition

polymerization is impossible in this crystal. Among the powder

X-ray diﬀractograms of the compounds with other trialkox-

yphenyl groups, C O-0 and C O-0 showed clear progression

Black, green, blue, violet, and red lines correspond to the spectra after

UV irradiation for 0, 5, 30, 120, and 480 min, respectively.

form 1D stacking along the b axis due to the intermolecular

hydrogen bonding between urethane groups (green dashed

lines in Figure 5b). The distance d and angle θ, deﬁned in

Figure 1, are 0.476 nm and 65.6°, respectively. In comparison

with the polymerizable conditions, d is slightly shorter and θ is

larger. The carbon−carbon (C−C) distances between adjacent

molecules are 0.438, 0.443, and 0.470 nm for C1−C2, C3−C4,

and C1−C4, respectively, whose carbon numbers are indicated

in Figure 5b. Namely, C−C distances for 1,2-addition (C1−C2

and C3−C4) are shorter than those of 1,4-addition (C1−C4).

of the peaks related to the layered structures, and the interlayer

spacings were calculated to be 5.00 and 5.99 nm, respectively.

In comparison with these, C O-0 showed weaker and broad

peaks, and the spacing was roughly estimated to be 4.4 nm.

Namely, longer alkyl chains of the compound tend to give a

larger spacing. C O-1, C O-1, and C O-1 showed much

weaker diﬀraction peaks, suggesting their lower crystallinity.

However, C O-1 showed a progression of the peaks

corresponding to a spacing of about 3.3 nm. Although the

peaks of C O-1 and C O-1 were broad, the spacings were

This result is clear evidence that C O-0 does not polymerize in

roughly estimated to be 3.2 and 6.8 nm, respectively. The

relationship between the alkyl chain length and the spacing of

C O-1 is similar to that of C O-0. However, the spacing of

the regular 1,4-addition manner, resulting in absorption spectra

of C O-0 without an excitonic peak after UV irradiation

(

Figure 3c). Unexpectedly for C O-1, there are no hydrogen

C O-1 is slightly more than twice the spacing of C O-1 or

C O-1. This may suggest that the periodic structure of C O-

12 16

bonds between urethane groups but the nitrogen atom of the

urethane group forms an intermolecular hydrogen bond with

the oxygen atom of a methoxy group (green dashed lines in

Figure 6a). As a result, the carboxy group in the urethane bond

1 is the bilayer type but that of C O-1 or C O-1 is the

monolayer type. The melting points of C O-0 are higher than

those of the corresponding C O-1, respectively, and these

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Figure 5. Crystal structure of C O-0 viewed along (a) the b axis and

(

b) the c axis. Green dashed lines in (b) indicate intermolecular

hydrogen bonds. Numbers labeling sp carbons in (b) are to enable an

explanation of the carbon−carbon distance in the text. Atom color

code: gray, blue, and red refer to carbon, nitrogen, and oxygen,

respectively.

diﬀerences may originate from the crystallinity. As described

above, C O-1 with less crystallinity regularly polymerized and

C O-0 with more crystallinity did not. This fact seems

Figure 6. Crystal structure of C O-1 viewed along (a) the a axis and

contradictory. However, a similar situation, i.e., polymerizable

butadiyne moieties in a less crystalline environment, can be

found in segmented copolymers composed of polyurethane or

(

b) the b axis. Green dashed lines in (a) indicate intermolecular

hydrogen bonds. In (b), red and blue rectangles indicate pyrene and

butadiyne moieties, respectively. Atom color code: gray, blue, and red

refer to carbon, nitrogen, and oxygen, respectively.

58−60

polyamide with butadiyne moieties in the backbone.

these polymers, the butadiyne moieties stacked regularly in the

hard segment, which are surrounded by the amorphous soft

segment, can polymerize in the 1,4-addition manner. In the

absorption maximum wavelength has been blue-shifted from

that in the crystalline state at 659 nm. This blue shift may be

due to less planarity of the π-conjugated backbone with the

solvated side chains. Photopolymerized C O-1 and C O-1

less crystalline C O-1, the butadiyne moieties are properly

aligned but the methylene group in the benzyl urethane moiety

may prevent an ordered assembling of the alkyl chains of

TAOP groups. The contrast in crystallinity between C O-0

were also soluble in chloroform. The chloroform solution of

−

and C O-1 are interesting, although the more detailed

the polymerized sample of C O-1 with 1 g L concentration,

structural diﬀerences were not able to be clariﬁed. Regardless

of polymerization in the regular manner or not, a close contact

of the pyrene moieties was conﬁrmed in the solid state of this

series of compounds because a broad emission attributed to

pyrene excimer formation was observed in the ﬂuorescence

spectra in the solid state (Figure S1).

which was ﬁltered by a membrane ﬁlter with a pore size of 0.45

μm, was subjected to GPC, and the elution curve in Figure 8

was obtained. The molecular weight distribution was quite

broad from the oligomer level to polymers with a molecular

weight of more than 1 × 10 , which is about the exclusion limit

of the columns. A dip in the elution curve at a retention time of

C O-1 after UV irradiation for 12 h was dissolved in

about 35 min corresponded to a molecular weight of about 6 ×

chloroform, and the solution was added dropwise in methanol

to reprecipitate. The yields of the polymer precipitated were

10 of the standard polystyrene. If the components are divided

at this molecular weight, the higher-molecular-weight

components accounted for about 60% of the product, which

is simply estimated by the area of the elution curve.

0−15%. The UV−vis spectrum of the resulting precipitate

portion (PC O-1) dissolved in chloroform is shown in Figure

. The absorption maximum at 612 nm of the PDA structure

In order to investigate the function of the pyrenyl group

introduced, experiments on chemical doping were performed.

was clearly observed even in chloroform, although the

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

1:1 molar ratio and the solvents were evaporated. Figure 9

Article

Table 1. Crystallographic Data of C O-0 and C O-1

Table 2. Electric Conductivities (σ) of C O-1, PC O-1,

and Their Charge-Transfer States

C O-0

C O-1

sample

donor

acceptor

I₂

σ/S m⁻

remark

formula

formula wt

cryst syst

space group

a/Å

b/Å

c/Å

α/deg

β/deg

C H NO

489.50

C H NO₅

32 25

2.3 × 10⁻

8.4 × 10⁻

pristine

503.53

triclinic

C O-1

monoclinic

P2₁/_C

22.7495(13)

4.7604(3)

22.7650(13)

106.637(4)

2362.2(2)

I vapor treatment of

sample 1a

1.7 × 10⁻

sample 1b kept in air to

8.030(13)

8.963(16)

17.65(4)

101.61(8)

92.09(6)

92.97(6)

1241(4)

remove I

C O-1

F₄TCNQ

1.4 × 10⁻

1:1 molar ratio

pristine

I vapor treatment of

sample 3a

PC O-1

1.9 × 10⁻

1.2 × 10⁻

γ/deg

_V_/_Å3

^I2

₅_.₀_×₁₀−8

sample 3b kept in air to

remove I

−

D /Mg m

1.376

1.347

R_w

GOF

T /K

0.0483

0.1102

1.057

0.0669

0.1470

0.988

1.3 × 10⁻

1:1 molar ratio

PC12O-1

TCNQ

90(2)

100(2)

and PC O-1 are within the range but are relatively high.

During iodine doping, the conductivities of C O-1 and

PC O-1 increased, and they were ﬁnally saturated at 8.4 ×

−

−2

−1

and 1.2 × 10 S m , respectively. Due to the conjugated

backbone of PC O-1, about a 2 orders of magnitude

conductivity enhancement was conﬁrmed, in comparison

with C O-1. Since pyrene is an electron donor and charge-

transfer (CT) complexes of pyrene and 7,7,8,8-tetracyanoqui-

68−73

nodimethane (TCNQ) derivatives have been known,

prepared CT complexes of C O-1 and PC O-1 with 2,3,5,6-

tetraﬂuoro-7,7,8,8-tetracyanoquinodimethane (F TCNQ). For

the CT complex preparation, chloroform solutions of C O-1

Figure 7. UV−vis absorption spectrum of the chloroform solution of

PC O-1 (blue curve). A magniﬁed spectrum is shown between 450

and 750 nm using a black curve. The solution measured was prepared

or PC O-1 were mixed with F TCNQ acetone solution in a

as follows: C O-1 after irradiation of UV at 254 nm for 12 h was

dissolved in chloroform, and the resulting solution was ﬁltered by a

membrane ﬁ lter with a pore size of 0.45 μ m.

Figure 9. UV−vis−NIR diﬀuse reﬂectance spectra of CT complexes

with F TCNQ: (a) C O-1/F TCNQ; (b) PC O-1/F TCNQ. The

molar ratio of F TCNQ with respect to C O-1 and the PC O-1

monomer unit was 1:1.

shows UV−vis−NIR diﬀuse reﬂectance spectra of the

complexes C O-1/F TCNQ and PC O-1/F TCNQ. In the

Figure 8. GPC elution curve of polymerized C O-1.

spectrum of C O-1/F TCNQ, a broad CT band from around

200 nm to the visible region was observed. Although C O-1/

By using C O-1 as a base compound, the four ﬁlm samples,

F₄TCNQ was irradiated at a UV wavelength of 254 nm,

apparent spectral changes were not detected, indicating that

the complex is photostable and not polymerizable. The

spectrum of PC O-1/F TCNQ also showed a broad CT

which were generally amorphous, were prepared on glass slides

with gold electrodes, and their DC electrical conductivities

were evaluated by the two-probe method (Table 2). Sample 1a

was prepared by casting a C O-1 chloroform solution. Iodine

band from the NIR to visible region, but it seemed to be

vapor treatment of sample 1a gave sample 1b, and sample 1c

was obtained by keeping sample 1b in air for a prolonged time

to remove iodine. Similar samples 3a−c were prepared for the

corresponding PDA of PC O-1. Before iodine treatment and

weaker than that of C O-1/F TCNQ. Since the peak at

approximately 600 nm remained, the PDA backbone structure

was considered to be maintained. The conductivities of C O-

1/F TCNQ and PC O-1/F TCNQ were evaluated to be 1.4

−

−4

−1

after removal of iodine, the conductivities of C O-1 and

× 10 and 1.3 × 10 S m , respectively. When the

conductivities were compared between iodine-doped and CT-

complexed samples, higher conductivities were obtained for

the former samples of both the monomer and polymer,

−

−7

PC O-1 at room temperature were on the order of 10 −10

S m . Since the conductivities of pristine PDAs are reported

−

to be on the order of 10⁻−10 S m ,

−7

−1 61−67

those of C O-1

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

−

indicating that better CT states for electric conduction were

achieved in iodine doping in these cases. For the iodine-doped

PDAs in general, the conductivities have been reported to be

IR (KBr) 3305, 3035, 2978, 2931, 1162, 964, 845, 715 cm ; H

NMR (400 MHz, CDCl ) δ 1.79 (6H, s), 2.77 (1H, br s), 7.80−8.03

(

8H, m), 8.46 (1H, d, J = 8.8 Hz); C NMR (100 MHz, CDCl ) δ

31.67, 65.94, 81.15, 99.35, 116.93, 123.96, 124.08, 124.17, 125.07,

25.31, 125.36, 125.94, 126.93, 127.85, 128.07, 129.39, 130.73,

30.92, 130.95, 131.66.

-Ethynylpyrene (3). A mixture of 2 (4.90 g, 17.2 mmol) and

mashed potassium hydroxide (0.981g, 17.5 mmol) in toluene (100

mL) was reﬂuxed for 30 min. After ﬁltration, the solvent in the ﬁltrate

was removed under reduced pressure. The residue was puriﬁed by

column chromatography (silica gel, chloroform) to aﬀord 3 (3.62 g,

6.0 mmol, 93%) as a brown solid: mp 115 °C; IR (KBr) 3296, 3033,

094, 1600, 839, 714, 644, 593 cm ; H NMR (400 MHz, CDCl ) δ

−

−4

−1 32−37,62

on the order of 10 −10 S m .

By using other

dopants and polymerization under high pressure, the

conductivities of PDA increased up to 10⁻S m . In the

−1 74

present study, the conductivity of the iodine-doped PC O-1

was measured to be as high as 10⁻S m , which may be due

to an appropriate charge transfer from the pyrene moieties to

iodine molecules and eﬀective π conjugation between the

pyrene moieties and the PDA backbone.

−1

−

1 1

.56 (1H, s), 7.82−8.06 (8H, m), 8.46 (1H, d, J = 9.2 Hz); C NMR

(100 MHz, CDCl ) δ 82.45, 82.75, 116.28, 123.93, 124.08, 124.19,

125.08, 125.49, 125.55, 126.06, 126.94, 128.18, 128.35, 129.96,

CONCLUSION

■

Ten pyrenyl-substituted PDAs with a urethane moiety were

prepared. Regular 1,4-addition polymerization was conﬁrmed

for H-0, H-1, C O-1, C O-1, and C O-1, which showed

30.74, 130.93, 131.36, 132.29.

-(Pyren-1-yl)penta-2,4-diyn-1-ol (4). A mixture of copper(I)

chloride (43.8 mg, 0.442 mmol) and a spatulafull of hydroxylammo-

nium chloride in isopropylamine (30 mL) was stirred under a

nitrogen atmosphere. To this were added 3-bromoprop-2-yn-1-ol

characteristic excitonic absorption peaks between 646 and 691

nm. Although C O-0 and C O-1 were not polymerized in the

regular manner, the crystal structures were able to be analyzed

and the reasons they did not regularly polymerize were

(

2.20 g 16.3 mmol) and 3 (2.00 g 8.84 mmol) in 28 mL of anhydrous

tetrahydrofuran (THF) dropwise for 30 min. When the mixture

became dark during the addition, a small amount of hydroxyammo-

nium chloride was added until the mixture turned yellow. This

mixture was further stirred overnight. After the solvent in the reaction

mixture was removed, chloroform was added and this solution was

washed with water. The organic layer was dried over anhydrous

sodium sulfate. After ﬁltration, the solvent in the ﬁltrate was removed

under reduced pressure. The residue was puriﬁed by column

chromatography (silica gel, chloroform/ethyl acetate 9/1) and

recrystallized from a mixture of chloroform and hexane to aﬀord 4

clariﬁed. For C O-0, 1D monomer arrays due to the

intermolecular hydrogen bonding between urethane groups

were formed. However, d was shorter and θ was larger with

respect to the regularly polymerizable conditions. For C O-1,

intermolecular hydrogen bonding was not formed between

urethane groups but formed between urethane and methoxy

groups, which resulted in alternating stacking of pyrene and

butadiyne moieties. Although the introduction of a urethane or

amide group in butadiyne monomers promotes the formation

of 1D arrays in the crystals in general, this principle is

sometimes broken. For longer alkyl derivatives, crystallinities of

C O-1 were lower than those of C O-0 despite the regular

(

0.82 g, 2.93 mmol, 33%) as a pale orange powder: mp 123 °C dec;

IR (KBr) 3367, 3035, 2917, 2852, 2227, 1600, 1596, 1392, 1007, 839,

713 cm ; H NMR (400 MHz, CDCl ) δ 1.92 (1H, br s), 4.52 (2H,

−1 1

s), 7.94−8.18 (8H, m), 8.47 (1H, d, J = 9.2 Hz); C NMR (100

MHz, CDCl ) δ 51.83, 70.86, 78.06, 78.41, 81.84, 115.42, 123.93,

24.14, 124.40, 125.03, 125.84, 125.90, 126.30, 127.03, 128.72,

28.81, 130.49, 130.80, 131.00, 131.83, 133.32.

-(Pyren-1-yl)penta-2,4-diynyl N-Phenylcarbamate (H-0). A

mixture of 4 (50.0 mg, 0.178 mmol), phenyl isocyanate (27.2 mg,

.228 mmol), and a few drops of dibutyltin dilaurate in anhydrous

THF (20 mL) was stirred overnight at ambient temperature. After the

solvent was removed under reduced pressure, the residue was puriﬁed

by column chromatography (silica gel, chloroform/ethyl acetate 9/1)

and recrystallized from a mixture of chloroform and hexane to aﬀord

H-0 (60.0 mg, 0.150 mmol, 84%) as a pale yellow powder: mp 167

polymerization of C O-1. This fact indicates that local

ordering around 1D arrays for the polymerization direction

may not be reﬂected in the total crystallinity. Polymerized

C O-1 is soluble in chloroform and processable. Solution-cast

ﬁlms of C O-1, PC O-1, and their CT complexes with

F TCNQ were prepared. For the C O-1 and PC O-1 ﬁlms,

iodine doping was performed and their conductivities were

evaluated. The highest conductivity among the measured

conditions was 1.2 × 10⁻S m for iodine-doped PC O-1, in

−1

which appropriate charge transfer and eﬀective π conjugation

between the substituents and the PDA backbone seemed to be

achieved.

C; IR (KBr) 3294, 3032, 2920, 2235, 1695, 1552, 1448, 1358, 1255,

135, 1055, 978, 850, 754, 698 cm ; H NMR (400 MHz, CDCl ) δ

.03 (2H, s), 6.77 (1H, br s), 7.11 (1H, t, J = 7.2 Hz), 7.34 (2H, t, J =

−

1 1

.2 Hz), 7.43 (2H, d, J = 7.2 Hz), 8.00−8.23 (8H, m), 8.51 (1H, d, J

EXPERIMENTAL SECTION

■

= 9.0 Hz); C NMR (100 MHz, CDCl

) δ 53.54, 71.76, 77.72, 78.30,

Materials. Commercially available reagents and solvents were used

as received except for copper(I) chloride, which was washed with

hydrochloric acid (2 mol/L) and vacuum-dried in an oven at 100 °C.

The synthesis procedures of alkoxy-substituted phenyl isocyanates

a −d and benzyl isocyanates 15a−d are described in the Supporting

Information .

78.40, 115.25, 118.76, 123.89, 124.00, 124.22, 124.42, 125.10, 125.95,

126.01, 126.40, 127.10, 128.88, 128.95, 129.14, 130.64, 130.87,

131.06, 132.01, 133.50, 137.31, 152.32. Anal. Found: C, 83.84; H,

4.07; N, 3.48. Calcd for C28H17NO : C, 84.19; H, 4.29; N, 3.51.

5-(Pyren-1-yl)penta-2,4-diynyl N-Benzylcarbamate (H-1). A

mixture of 4 (320 mg, 1.14 mmol), benzyl isocyanate (197 mg, 1.47

mmol), and a few drops of dibutyltin dilaurate in anhydrous THF (20

mL) was stirred overnight at ambient temperature. After the solvent

was removed, the residue was puriﬁed by column chromatography

(silica gel, chloroform/ethyl acetate 9/1) and recrystallized from a

mixture of chloroform and hexane to aﬀord H-1 (380 mg, 0.919

mmol, 81%) as an orange powder: mp 148 °C; IR (KBr) 3294, 3029,

2920, 2233, 1695, 1550, 1448, 1357, 1254, 1134, 1053, 976, 850, 756,

698 cm ; H NMR (400 MHz, CDCl ) δ 4.41 (2H, d, J = 5.9 Hz),

4.95 (2H, s), 5.22 (1H, br s), 7.26−7.36 (5H, m), 7.92−8.17 (8H,

m), 8.44 (1H, d, J = 9.1 Hz); C NMR (100 MHz, CDCl ) δ 45.23,

53.39, 71.42, 78.17, 78.21, 78.39, 115.24, 123.88, 124.09, 124.32,

125.01, 125.84, 125.91, 126.29, 126.99, 127.52, 127.59, 128.70,

2-Methyl-4-(pyren-1-yl)but-3-yn-2-ol (2). A mixture of 1-

bromopyrene (1; 5.00 g, 17.8 mmol) and bis(triphenylphosphine)-

palladium(II) dichloride (0.19 g, 0.27 mmol) in diethylamine (26

mL) was stirred at 50 °C until all compounds were dissolved. Then, 2-

methyl-3-butyn-2-ol (1.85 mL, 18.9 mmol) and copper(I) iodide

(

51.4 mg, 0.27 mmol) were added, and the mixture was reﬂuxed

overnight. After the solvent was removed from the reaction mixture,

chloroform was added and washed with water. The organic layer was

dried over anhydrous sodium sulfate, and the solvent in the ﬁltrate

was removed under reduced pressure. The residue was puriﬁed by

column chromatography (silica gel, chloroform/ethyl acetate 9/1) to

aﬀord 2 (4.90 g, 17.2 mmol, 97%) as a dark orange solid: mp 116 °C;

−

1 1

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

28.74, 128.82, 130.53, 130.77, 130.97, 131.87, 133.36, 137.97,

55.42. Anal. Found: C, 84.16; H, 4.42; N, 3.39. Calcd for

solvent in the reaction mixture was removed, the residue was puriﬁed

by column chromatography (silica gel, chloroform) and recrystallized

C H NO : C, 84.24; H, 4.63; N, 3.39.

from a mixture of chloroform and methanol to aﬀord C O-0 (100

-(Pyren-1-yl)penta-2,4-diynyl N-(3,4,5-Trimethoxyphenyl)-

mg, 0.0892 mmol, 25%) as a pale orange solid: mp 109 °C; IR (KBr)

carbamate (C O-0). A mixture of 4 (100 mg, 0.357 mmol), crude

3290, 3045, 2916, 2848, 2231, 1693, 1599, 1537, 1466, 1431, 1383,

−

,4,5-trimethoxyphenyl isocyanate (9a; 1.64 g), and a few drops of

1344, 1298, 1227, 1120, 1081, 1016, 987, 843, 765, 715 cm ; H

dibutyltin dilaurate in anhydrous THF (30 mL) was stirred overnight

at ambient temperature. After the solvent in the reaction mixture was

removed, the residue was puriﬁed by column chromatography (silica

gel, chloroform/ethyl acetate 9/1) and recrystallized from a mixture

NMR (600 MHz, CDCl ) δ 0.85−0.90 (9H, m), 1.21−1.36 (72H,

m), 1.42−1.50 (6H, m), 1.72−1.82 (6H, m), 3.91 (2H, t, J = 6.5 Hz),

3.97 (6H, t, J = 6.5 Hz), 5.00 (2H, s), 6.61 (1H, s), 6.66 (2H, s),

8.03−8.26 (8H, m), 8.53 (1H, d, J = 9.0 Hz); C NMR (150 MHz,

of chloroform and methanol to aﬀord C O-0 (110 mg, 0.225 mmol,

CDCl ) δ 14.11, 22.68, 26.08, 26.14, 29.37*, 29.42*, 29.64*, 29.71*,

3%) as a pale orange powder: mp 193 °C; IR (KBr) 3294, 3051,

29.75*, 30.29, 31.92, 53.46, 69.14, 71.73, 73.52, 77.77, 78.33, 78.41,

97.84, 115.31, 124.06, 124.30, 124.45, 125.13, 125.99, 126.05, 126.44,

127.13, 128.92, 128.99, 130.67, 130.93, 131.13, 132.07, 132.83,

133.55, 134.57, 152.37, 153.34. Asterisks indicate overlapped peaks.

Anal. Found: C, 81.44; H, 10.20; N, 1.23. Calcd for C H NO : C,

937, 2835, 2231, 1695, 1601, 1545, 1510, 1454, 1415, 1352, 1304,

−

1 1

236, 1169, 1134, 1080, 1005, 978, 843, 764, 714 cm ; H NMR

(

600 MHz, CDCl ) δ 3.82 (3H, s), 3.86 (6H, s), 5.02 (2H, s), 6.71

2H, s), 6.72 (1H, s), 8.01−8.22 (8H, m), 8.50 (1H, d, J = 8.4 Hz);

113

C NMR (150 MHz, CDCl ) δ 53.53, 56.12, 60.98, 71.80, 77.68,

81.45; H, 10.16; N, 1.25.

5 - ( P y r e n - 1 - y l ) p e n t a - 2 , 4 - d i y n y l N - [ ( 3 , 4 , 5 -

Trimethoxyphenyl)methyl]carbamate (C O-1). A mixture of 4

8.29, 78.48, 96.54, 115.22, 124.01, 124.24, 124.42, 125.07, 125.98,

26.03, 126.42, 127.10, 128.91, 128.97, 130.64, 130.88, 131.08,

32.06, 133.44, 133.51, 134.38, 152.45 153.48. HRMS (ESI/Q-TOF)

(0.100 g, 0.357 mmol), crude (3,4,5-trimethoxyphenyl)methyl

isocyanate (15a; 0.440 g), and a few drops of dibutyltin dilaurate in

anhydrous THF (30 mL) was stirred overnight at ambient

temperature. After the solvent in the reaction mixture was removed,

the residue was puriﬁed by column chromatography (silica gel,

chloroform/ethyl acetate 9/1) and recrystallized from a mixture of

m/z: [M + Na] calcd for C H NO Na 512.1468; found 512.1486.

-(Pyren-1-yl)penta-2,4-diynyl N-(3,4,5-Trioctyloxyphenyl)-

carbamate (C O-0). A mixture of 4 (100 mg, 0.357 mmol), crude

,4,5-trioctyloxyphenyl isocyanate (9b; 0.620 g), and a few drops of

dibutyltin dilaurate in anhydrous THF (30 mL) was stirred overnight

at ambient temperature. After the solvent in the reaction mixture was

removed, the residue was puriﬁed by column chromatography (silica

gel, chloroform) and recrystallized from a mixture of chloroform and

chloroform and methanol to aﬀord C O-1 (100 mg, 0.199 mmol,

56%) as an orange powder: mp 164 °C; IR (KBr) 3311, 3047, 2925,

2231, 1722, 1597, 1508, 1464, 1423, 1377, 1329, 1244, 1126, 1038,

−

1 1

methanol to aﬀord C O-0 (230 mg, 0.293 mmol, 82%) as a pale

993, 845, 777, 715 cm ; H NMR (600 MHz, CDCl ) δ 3.83 (3H,

orange powder: mp 106 °C; IR (KBr) 3303, 3041, 2954, 2924, 2852,

s), 3.87 (6H, s), 4.36 (2H, d, J = 6.0 Hz), 4.97 (2H, s), 5.23 (1H, s),

231, 1697, 1601, 1540, 1508, 1468, 1433, 1379, 1348, 1300, 1240,

6.54 (2H, s), 8.01−8.23 (8H, m), 8.50 (1H, d, J = 9.0 Hz); C NMR

−

1 1

176, 1132, 1080, 1020, 989, 847, 820, 760, 714 cm ; H NMR (600

(150 MHz, CDCl ) δ 45.55, 53.41, 56.13, 60.81, 71.38, 78.21, 78.35,

MHz, CDCl ) δ 0.85−0.91 (9H, m), 1.19−1.39 (24H, m), 1.44−1.50

104.49, 115.27, 124.01, 124.25, 124.41, 125.04, 125.95, 126.00,

126.40, 127.09, 128.88, 128.95, 130.60, 130.88, 131.08, 132.03,

133.47, 133.77, 137.38, 153.44, 155.44. HRMS (ESI/Q-TOF) m/z:

(

6H, m), 1.73 (2H, tt, J = 7.2 Hz, 7.2 Hz), 1.79 (4H, tt, J = 7.2 Hz,

.2 Hz), 3.91 (2H, t, J = 7.2 Hz), 3.96 (6H, t, J = 7.2 Hz), 5.00 (2H,

s), 6.64 (1H, s), 6.66 (2H, s), 8.02−8.25 (8H, m), 8.52 (1H, d, J = 9.0

[M + Na] calcd for C H NO Na 526.1625; found 526.1631.

Hz); ¹³C NMR (150 MHz, CDCl ) δ 14.10, 22.66, 22.69, 26.06,

5-(Pyren-1-yl)penta-2,4-diynyl N-[(3,4,5-Trioctyloxyphenyl)-

6.12, 29.28*, 29.33*, 29.36*, 29.56*, 30.28, 31.82, 31.90, 53.45,

9.11, 71.72, 73.52, 77.78, 78.32, 78.40, 97.83, 115.28, 124.03, 124.27,

24.44, 125.11, 125.98, 126.03, 126.43, 127.11, 128.91, 128.98,

30.66, 130.91, 131.10, 132.06, 132.84, 133.53, 134.51, 152.44,

53.33. Asterisks indicate overlapped peaks. Anal. Found: C, 79.71;

methyl]carbamate (C O-1). A mixture of 4 (80.0 mg, 0.285 mmol),

crude (3,4,5-trioctyloxyphenyl)methyl isocyanate (15b; 0.270 g), and

a few drops of dibutyltin dilaurate in anhydrous THF (30 mL) was

stirred overnight at ambient temperature. After the solvent in the

reaction mixture was removed, the residue was puriﬁed by column

chromatography (silica gel, chloroform/ethyl acetate 9/1) and

recrystallized from a mixture of chloroform and methanol to aﬀord

H, 8.55; N, 1.75. Calcd for C H NO : C, 79.66; H, 8.36; N, 1.79.

- ( P y r e n - 6 - y l ) p e n t a - 2 , 4 - d i y n y l N - ( 3 , 4 , 5 -

Tridodecyloxyphenyl)carbamate (C O-0). A mixture of 4 (200

C O-1 (120 mg, 0.150 mmol, 53%) as a yellowish green solid: mp

mg, 0.713 mmol), crude 3,4,5-tridodecyloxyphenyl isocyanate (9c;

.961 g), and a few drops of dibutyltin dilaurate in anhydrous THF

30 mL) was stirred overnight at ambient temperature. After the

105 °C; IR (KBr) 3307, 3043, 2921, 2850, 2235, 1693, 1592, 1552,

(

1508, 1442, 1383, 1331, 1277, 1228, 1119, 1054, 978, 845, 754, 715

−

1 1

cm ; H NMR (600 MHz, CDCl ) δ 0.83−0.89 (9H, m), 1.17−1.35

solvent in the reaction mixture was removed, the residue was puriﬁed

by column chromatography (silica gel, chloroform) and recrystallized

from a mixture of chloroform and methanol to aﬀord C O-0 (470

(24H, m), 1.40−1.49 (6H, m), 1.69−1.81 (6H, m), 3.92 (2H, t, J =

6.6 Hz), 3.96 (4H, t, J = 6.6 Hz), 4.32 (2H, d, J = 6.0 Hz), 4.96 (2H,

s), 5.14 (1H, t, J = 6.0 Hz), 6.49 (2H, s), 8.00−8.24 (8H, m), 8.50

mg, 0.493 mmol, 69%) as a pale orange powder: mp 104 °C; IR

KBr) 3288, 3045, 2917, 2850, 2231, 1693, 1601, 1539, 1465, 1431,

382, 1346, 1298, 1230, 1178, 1120, 1080, 1020, 985, 843, 760, 715

(1H, d, J = 8.4 Hz); C NMR (150 MHz, CDCl ) δ 14.07, 22.63,

(

22.66, 26.08, 29.26*, 29.35*, 29.39*, 29.53*, 30.29, 31.79, 31.87,

45.60, 53.37, 69.11, 71.36, 73.41, 78.16, 78.25, 78.38, 105.92, 115.31,

124.00, 124.23, 124.41, 125.08, 125.93, 125.99, 126.39, 127.09,

128.86, 128.93, 130.61, 130.88, 131.07, 132.00, 133.02, 133.47,

137.52, 153.32, 155.37. Asterisks indicate overlapped peaks. Anal.

Found: C, 79.48; H, 8.70; N, 1.75. Calcd for C H NO : C, 79.76;

−

1 1

cm ; H NMR (400 MHz, CDCl ) δ 0.87 (9H, t, J = 6.8 Hz), 1.16−

.37 (48H, m), 1.43−1.48 (6H, m), 1.71−1.80 (6H, m), 3.91 (2H, t, J

6.4 Hz), 3.95 (6H, t, J = 6.6 Hz), 5.00 (2H, s), 6.66 (2H, s), 6.68

(

1H, br s), 7.99−8.22 (8H, m), 8.50 (1H, d, J = 9.2 Hz); C NMR

100 MHz, CDCl ) δ 14.12, 22.68, 26.07, 26.12, 29.32*, 29.36*,

H, 8.46; N, 1.75.

9.38*, 29.40*, 29.63*, 29.69*, 29.75*, 30.27, 53.43, 69.05, 71.71,

3.49, 77.74, 78.30, 78.38, 97.74, 115.22, 123.98, 124.20, 124.40,

25.06, 125.93, 126.00, 126.38, 127.07, 128.87, 128.94, 130.60,

30.84, 131.04, 132.00, 132.85, 133.47, 134.40, 152.42, 153.30.

5 - ( P y r e n - 1 - y l ) p e n t a - 2 , 4 - d i y n y l N - [ ( 3 , 4 , 5 -

Tridodecyloxyphenyl)methyl]carbamate (C12O-1). A mixture

of 4 (300 mg, 1.07 mmol), crude (3,4,5-tridodecyloxyphenyl)methyl

isocyanate (15c; 1.36 g), and a few drops of dibutyltin dilaurate in

anhydrous THF (30 mL) was stirred overnight at ambient

temperature. After the solvent in the reaction mixture was removed,

the residue was puriﬁed by column chromatography (silica gel,

chloroform/ethyl acetate 9/1) and recrystallized from a mixture of

chloroform and methanol to aﬀord C O-1 (540 mg, 0.559 mmol,

Asterisks indicate overlapped peaks. Anal. Found: C, 80.50; H, 9.68;

N, 1.41. Calcd for C H NO : C, 80.71; H, 9.42; N, 1.47.

- ( P y r e n - 1 - y l ) p e n t a - 2 , 4 - d i y n y l N - ( 3 , 4 , 5 -

Trihexadecyloxyphenyl)carbamate (C O-0). A mixture of 4

(

100 mg, 0.357 mmol), crude 3,4,5-trihexadecyloxyphenyl isocyanate

9d; 1.19 g), and a few drops of dibutyltin dilaurate in anhydrous

52%) as a yellowish green solid: mp 97 °C; IR (KBr) 3309, 3009,

2920, 2850, 2237, 1693, 1593, 1552, 1508, 1468, 1439, 1387, 1331,

THF (20 mL) was stirred overnight at ambient temperature. After the

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

https://pubs.acs.org/doi/10.1021/acs.cgd.0c00438.

Article

−

1 1

265, 1220, 1055, 973, 843, 714 cm ; H NMR (600 MHz, CDCl )

deposition equipment (ULVAC Kiko), and chloroform solutions of

the compounds were cast on the slides to form the ﬁlms. The ﬁlm

thickness was measured using a Surfcoder ET200 microﬁgure

measuring instrument (Kosaka Laboratory).

δ 0.85−0.89 (9H, m), 1.16−1.34 (48H, m), 1.41−1.48 (6H, m),

(

.69−1.81 (6H, m), 3.92 (2H, t, J = 6.6 Hz), 3.97 (4H, t, J = 6.6 Hz),

.32 (2H, d, J = 5.7 Hz), 4.96 (2H, s), 5.12 (1H, t, J = 5.7 Hz), 6.49

2H, s), 8.02−8.25 (8H, m), 8.52 (1H, d, J = 9.0 Hz); C NMR (150

MHz, CDCl ) δ 14.10, 22.67, 26.10, 29.35*, 29.38*, 29.41*, 29.62*,

9.67*, 29.74*, 30.31, 31.90, 45.61, 53.38, 69.15, 71.37, 73.42, 78.18,

8.25, 78.41, 105.97, 115.36, 124.05, 124.28, 124.43, 125.12, 125.96,

26.02, 126.41, 127.11, 128.89, 128.96, 130.64, 130.92, 131.12,

32.04, 133.02, 133.52, 137.60, 153.35, 155.37. Asterisks indicate

ASSOCIATED CONTENT

■

sı Supporting Information

The Supporting Information is available free of charge at

overlapped peaks. Anal. Found: C, 80.59; H, 9.55; N, 1.36. Calcd for

C H NO : C, 80.78; H, 9.49; N, 1.45.

Fluorescence spectra and synthesis of phenyl and benzyl

isocyanates (PDF)

- ( P y r e n - 1 - y l ) p e n t a - 2 , 4 - d i y n y l N - [ ( 3 , 4 , 5 -

Trihexadecyloxyphenyl)methyl]carbamate (C O-1). A mixture

Accession Codes

of 4 (80.0 mg, 0.285 mmol), crude (3,4,5-trihexadecyloxyphenyl)-

methyl isocyanate (15d; 0.500 g), and a few drops of dibutyltin

dilaurate in anhydrous THF (30 mL) was stirred overnight at ambient

temperature. After the solvent in the reaction mixture was removed,

the residue was puriﬁed by column chromatography (silica gel,

chloroform/ethyl acetate 9/1) and recrystallized from a mixture of

chloroform and methanol to aﬀord C O-1 (80.0 mg, 0.0705 mmol,

CCDC 1993204−1993205 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.

5%) as a yellowish green solid: mp 78 °C; IR (KBr) 3307, 3043,

AUTHOR INFORMATION

Corresponding Author

918, 2848, 2237, 1693, 1592, 1554, 1508, 1468, 1439, 1385, 1331,

■

−

1 1

267, 1230, 1122, 1055, 968, 842, 715 cm ; H NMR (600 MHz,

CDCl ) δ 0.87 (9H, t, J = 6.9 Hz), 1.17−1.34 (72H, m), 1.40−1.48

Shuji Okada − Graduate School of Organic Materials Science

and Faculty of Engineering, Yamagata University, Yonezawa

(

6H, m), 1.69−1.81 (6H, m), 3.92 (2H, t, J = 6.6 Hz), 3.97 (4H, t, J =

.6 Hz), 4.32 (2H, d, J = 5.6 Hz), 4.96 (2H, s), 5.11 (1H, t, J = 5.6

92-8510, Japan; orcid.org/0000-0001-9519-6648;

Hz), 6.49 (2H, s), 8.02−8.25 (8H, m), 8.53 (1H, d, J = 9.0 Hz);

NMR (150 MHz, CDCl ) δ 14.10, 22.68, 26.11, 29.36*, 29.42*,

Email: okadas@yz.yamagata-u.ac.jp

9.63*, 29.65*, 29.70*, 29.74*, 30.31, 31.91, 45.61, 53.38, 69.15,

1.37, 73.42, 78.18, 78.25, 78.40, 105.95, 115.36, 124.05, 124.28,

24.43, 125.12, 125.96, 126.02, 126.42, 127.11, 128.89, 128.96,

30.65, 130.92, 131.12, 132.04, 133.03, 133.52, 137.58, 153.34,

55.37. Asterisks indicate overlapped peaks. Anal. Found: C, 81.20;

Authors

Shuhei Oshimizu − Graduate School of Organic Materials

Science, Yamagata University, Yonezawa 992-8510, Japan

Shoko Takeshi − Faculty of Engineering, Yamagata University,

Yonezawa 992-8510, Japan

Tsubasa Sato − Faculty of Engineering, Yamagata University,

Yonezawa 992-8510, Japan

Ryohei Yamakado − Graduate School of Organic Materials

Science and Faculty of Engineering, Yamagata University,

Yonezawa 992-8510, Japan; orcid.org/0000-0003-4085-

H, 10.89; N, 1.41%. Calcd for C H NO : C, 81.50; H, 10.21; N,

115

.23.

Characterization Methods and Apparatus. UV−vis diﬀuse

reﬂectance and absorption spectra were measured using a Jasco V-570

spectrophotometer, and an integrated sphere (ILN-472) was attached

to obtain the diﬀuse reﬂectance spectra. The samples for the diﬀuse

reﬂectance spectra were prepared by grinding solid compounds with

potassium bromide, and the mixtures were placed in a sample cell

with a quartz window for the measurements. FT-IR spectra were

recorded on a Horiba FT-720 spectrometer. Melting points were

226

Yoko Tatewaki − Division of Applied Chemistry, Tokyo

University of Agriculture and Technology, Koganei 184-8588,

Japan

measured using a SII TG/DTA 6200 calorimeter. H and C NMR

spectra were measured using a JEOL ECX-400 or ECZ-600

spectrometer. Elemental analyses were performed on a PerkinElmer

CHN/O 2400 II analyzer. High-resolution electrospray ionization

time-of-ﬂight mass spectrometry (ESI-TOF-MS) was obtained by

using a Bruker micrOTOF-Q II mass spectrometer in the positive ion

mode.

Complete contact information is available at:

https://pubs.acs.org/10.1021/acs.cgd.0c00438

Notes

The authors declare no competing ﬁnancial interest.

Powder X-ray diﬀraction patterns were measured using a

synchrotron radiation X-ray beam with a wavelength of 1.00 Å at

the BL40B2 beamline at SPring-8 (Hyogo, Japan). Single crystals of

C O-0 and C O-1 were obtained by the slow evaporation of a

ACKNOWLEDGMENTS

The synchrotron radiation experiments were performed at the

BL40B2 (2017B1294), BL02B1 (2018B1714) and BL40XU

■

solution of a chloroform/methanol (1/1) mixture. X-ray crystallo-

(

2019A1211) of SPring-8 with the approval of the Japan

graphic analyses of C O-0 and C O-1 were performed at the

Synchrotron Radiation Research Institute (JASRI) with the

supports by Dr. Noboru Ohta, JASRI/SPring-8, Dr. Kunihisa

Sugimoto, JASRI/SPring-8, and Dr. Nobuhiro Yasuda, JASRI/

SPring-8.

beamlines of BL40XU with an X-ray wavelength of 0.78192 Å and

BL02B1 with that of 0.4249 Å, respectively, at SPring-8 (Hyogo,

Japan). The structures were solved by direct methods. All non-

hydrogen atoms were reﬁned anisotropically.

Photopolymeriation was performed by UV irradiation at 254 nm

using a 4 W lamp (UVP, UVG-11). GPC was performed using two

serially connected Tosoh TSKgel G4000H_H_Rcolumns with a Jasco

PU-980 pump and a UV-975 UV−vis detector. The eluent was

chloroform, and polystyrene was used as a molecular weight standard.

The electrical conductivity was evaluated for the cast ﬁlms at room

temperature from I−V curves measured using an apparatus based on a

Keithley 2400 SourceMeter. On glass slides, gold electrodes with an

electrode gap of 50 μm were prepared using VPC-060 vacuum

REFERENCES

(1) Sauteret, C.; Hermann, J.-P.; Frey, R.; Prader

■

e, F.; Ducuing, J.;

Baughman, R. H.; Chance, R. R. Optical Nonlinearities in One-

Dimensional-Conjugated Polymer Crystals. Phys. Rev. Lett. 1976, 36,

956−959.

(2) 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-

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

aration by Palladium-Catalyzed Coupling Reaction, Nonlinear Optical

Article

Properties, Doping, and Chemical Reactivity. Macromolecules 1994,

Polyaniline Nanocomposites Based Sensor Array for Breath Ammonia

Analysis. Portable E-nose Approach to Non-invasive Diagnosis of

Chronic Kidney Disease. Sens. Actuators, B 2018 , 274 , 616 −626.

(23) 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.

(24) Baughman, R. H.; Yee, K. C. Solid-State Polymerization of

Linear and Cyclic Acetylenes. Macromol. Rev. 1978 , 13 , 219 −239.

(25) 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.

(26) Carter, G. M.; Hryniewicz, J. V.; Thakur, M. K.; Chen, Y. J.;

Meyler, S. E. Nonlinear Optical Processes in a Polydiacetylene

Measured with Femtosecond Duration Laser Pulses. Appl. Phys. Lett.

1986, 49, 998−1000.

(27) Hattori, T.; Kobayashi, T. Femtosecond Dephasing in a

Polydiacetylene Film Measured by Degenerate Four-Wave Mixing

with an Incoherent Nanosecond Laser. Chem. Phys. Lett. 1987, 133,

230−234.

(28) Kanetake, T.; Ishikawa, K.; Hasegawa, T.; Koda, T. Nonlinear

Optical Properties of Highly Oriented Polydiacetylene Evaporated

Films. Appl. Phys. Lett. 1989, 54, 2287−2289.

(

7, 6620−6626.

3) Hegde, P. K.; Adhikari, A. V.; Manjunatha, M. G.; Poornesh, P.;

Umesh, G. Third-Order Nonlinear Optical Susceptibilities of New

Copolymers Containing Alternate 3,4-Dialkoxythiophene and (1,3,4-

Oxadiazolyl)pyridine Moieties. Opt. Mater. 2009, 31, 1000−1006.

(

4) 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) . J. Chem. Soc., Chem.

Commun. 1977, 578−580.

5) Pron, A.; Rannou, P. Processible Conjugated Polymers: From

Organic Semiconductors to Organic Metals and Superconductors.

Prog. Polym. Sci. 2002, 27, 135−190.

6) Osaka, I.; McCullough, R. D. Advances in Molecular Design and

Synthesis of Regioregular Polythiophenes. Acc. Chem. Res. 2008, 41,

202−1214.

7) Kobayashi, T.; Yoneyama, H.; Tamura, H. Electrochemical

Reactions Concerned with Electrochromism of Polyaniline Film-

Coated Electrodes. J. Electroanal. Chem. Interfacial Electrochem. 1984,

(

77, 281−291.

8) Argun, A. A.; Aubert, P.-H.; Thompson, B. C.; Schwendeman, I.;

Gaupp, C. L.; Hwang, J.; Pinto, N. J.; Tanner, D. B.; MacDiarmid, A.

G.; Reynolds, J. R. Multicolored Electrochromism in Polymers:

Structures and Devices. Chem. Mater. 2004, 16, 4401−4412.

(29) Okada, S.; Ohsugi, M.; Masaki, A.; Matsuda, H.; Takaragi, S.;

Nakanishi, H. Preparation and Nonlinear Optical Property of

Polydiacetylenes from Unsymmetrical Diphenylbutadiynes with

Trifluoromethyl Substituents. Mol. Cryst. Liq. Cryst. 1990, 183, 81−

90.

9) Savagian, L. R.; Osterholm, A. M.; Shen, D. E.; Christiansen, D.

(

T.; Kuepfert, M.; Reynolds, J. R. Conjugated Polymer Blends for High

Contrast Black-to-Transmissive Electrochromism. Adv. Opt. Mater.

(

018, 6, 1800594.

10) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R.

(30) Rochford, K.; Zanoni, R.; Stegeman, G. I. Measurement of

Nonlinear Refractive Index and Transmission in Polydiacetylene

Waveguides at 1.319 μ m. Appl. Phys. Lett. 1991, 58, 13−15.

(31) Bakarezos, M.; Camacho, M. A.; Blewett, I. J.; Kar, A. K.;

Wherrett, B. S.; Matsuda, H.; Fukuda, T.; Yamada, S.; Rangel-Rojo,

R.; Katagi, H.; Kasai, H.; Okada, S.; Nakanishi, H. Ultrafast Nonlinear

Refraction in Integrated Fabry-Perot Etalon Containing Polydiacety-

lene. Electron. Lett. 1999, 35, 1078−1079.

(32) Se, K.; Ohnuma, H.; Kotaka, T. Electrical Conductivity of

Urethane-Substituted Poly(diacetylenes): Effect of Substituent Side

Groups and Molecular Weights. Macromolecules 1984, 17 (10),

2126−2131.

(33) Nakanishi, H.; Matsuda, H.; Kato, M. Preparation of a Variety

of Polymeric Conductors from Diacetylenes. Mol. Cryst. Liq. Cryst.

1984, 105, 77−88.

(34) Marikhin, V. A.; Guk, E. G.; Myasnikova, L. P. New Approach

to Achieving the Potentially High Conductivity of Polydiacetylene.

Phys. Solid State 1997, 39, 686−689.

(35) Matsuda, H.; Nakanishi, H.; Kato, S.; Kato, M. Conductivity of

Polydiacetylene with π -Conjugation between Polymer Backbone and

Substituents. J. Polym. Sci., Part A: Polym. Chem. 1987, 25, 1663−

1669.

N.; Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Light-

Emitting Diodes Based on Conjugated Polymers. Nature 1990, 347,

11) Kraft, A.; Grimsdale, A. C.; Holmes, A. B. Electroluminescent

39−541.

Conjugated Polymers −Seeing Polymers in a New Light. Angew.

Chem., Int. Ed. 1998, 37, 402−428.

12) 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.

(

13) 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) Facchetti, A. π -Conjugated Polymers for Organic Electronics

14) Gunes, S.; Neugebauer, H.; Sariciftci, N. S. Conjugated

Polymer-Based Organic Solar Cells. Chem. Rev. 2007, 107, 1324−

338.

and Photovoltaic Cell Applications. Chem. Mater. 2011, 23, 733−758.

16) 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,

(36) Shimada, S.; Masaki, A.; Matsuda, H.; Okada, S.; Nakanishi, H.

Molecular Architecture of Regularly Mixed π -Conjugated Systems

Using Diacetylene Solid-State Polymerization. Mol. Cryst. Liq. Cryst.

Sci. Technol., Sect. A 1998, 315, 83−92.

(37) Takami, K.; Kuwahara, Y.; Ishii, T.; Akai-Kasaya, M.; Saito, A.;

Aono, M. Significant Increase in Conductivity of Polydiacetylene

Thin Film Induced by Iodine Doping. Surf. Sci. 2005, 591, L273−

L279.

(38) Okada, S.; Peng, S.; Spevak, W.; Charych, D. Color and

Chromism of Polydiacetylene Vesicles. Acc. Chem. Res. 1998, 31,

229−239.

(39) Reppy, M. A.; Pindzola, B. A. Biosensing with Polydiacetylene

Materials: Structures, Optical Properties and Applications. Chem.

Commun. 2007, 42, 4317−4338.

17) Fuchigami, H.; Tsumura, A.; Koezuka, H. Polythienyleneviny-

37, 5759−5769.

lene Thin-Film Transistor with High Carrier Mobility. Appl. Phys.

Lett. 1993, 63, 1372−1374.

19) Lee, J.; Han, A.-R.; Kim, J.; Kim, Y.; Oh, J. H.; Yang, C.

18) Hamilton, M. C.; Kanicki, J. Organic Polymer Thin-Film

Transistor Photosensors. IEEE J. Sel. Top. Quantum Electron. 2004, 10,

40−848.

Solution-Processable Ambipolar Diketopyrrolopyrrole-Selenophene

Polymer with Unprecedentedly High Hole and Electron Mobilities.

J. Am. Chem. Soc. 2012, 134, 20713−20721.

Polymer-Based Chemical Sensors. Chem. Rev. 2000 , 100 , 2537 −2574.

20) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Conjugated

21) Janata, J.; Josowicz, M. Conducting Polymers in Electronic

Chemical Sensors. Nat. Mater. 2003, 2, 19−24.

22) Le Maout, P.; Wojkiewicz, J.-L.; Redon, N.; Lahuec, C.; Seguin,

F.; Dupont, L.; Mikhaylov, S.; Noskov, Y.; Ogurtsov, N.; Pud, A.

(40) Ahn, D. J.; Kim, J.-M. Fluorogenic Polydiacetylene Supra-

molecules: Immobilization, Micropatterning, and Application to

Label-Free Chemosensors. Acc. Chem. Res. 2008 , 41 , 805 −816.

(41) Jelinek, R.; Ritenberg, M. Polydiacetylene −Recent Molecular

Advances and Applications. RSC Adv. 2013, 3, 21192−21201.

Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

42) Orchard, B. J.; Tripathy, S. K. Molecular Structure and

(61) Day, D. R.; Lando, J. B. Conduction in Polydiacetylene

Bilayers. J. Appl. Polym. Sci. 1981, 26, 1605−1612.

Electronic Property Modification of Poly(diacetylenes). Macro-

molecules 1986, 19, 1844−1850.

(62) Se, K.; Ohnuma, H.; Kotaka, T. Urethane-Substituted

Polydiacetylenes: Structure and Electrical Properties of Poly[4,6-

decadiyne-1,10-diol bis[(n -butoxycarbonyl)methyl]urethane]. Macro-

molecules 1983, 16, 1581−1587.

43) Curtis, S. M.; Le, N.; Fowler, F. W.; Lauher, J. W. A Rational

Approach to the Preparation of Polydipyridyldiacetylenes: An

Exercise in Crystal Design. Cryst. Growth Des. 2005 , 5 , 2313 −2321.

44) Lauher, J. W.; Fowler, F. W.; Goroff, N. S. Single-Crystal-to-

Single-Crystal Topochemical Polymerizations by Design. Acc. Chem.

Res. 2008, 41, 1215−1229.

(

(63) Tanaka, Y.; Matsuda, H.; Iijima, S.; Fujikawa, H.; Nakanishi,

H.; Kato, M.; Kato, S. High Pressure Solid State Polymerization of

,4-Bis(p -toluenesulfonyloxymethyl)-1,3-butadiyne. Makromol. Chem.,

Rapid Commun. 1985, 6, 715−720.

64) Qian, R.; Shi, S.; Liu, T.; Zhu, D. Carrier Transport Properties

of Poly(1,6-bis-9-carbazolyl-2,4-hexadiyne). Phys. Status Solidi A

989, 111, K67−K71.

65) Takami, K.; Mizuno, J.; Akai-Kasaya, M.; Saito, A.; Aono, M.;

45) Nakanishi, H.; Matsuda, H.; Okada, S.; Kato, M. Preparation

46) Sarkar, A.; Okada, S.; Matsuzawa, H.; Matsuda, H.; Nakanishi,

and Nonlinear Optical Properties of Novel Polydiacetylenes. In

Frontiers of Macromolecular Science; Saegusa, T., Higashimura, T., Abe,

A., Eds.; Blackwell Scientiﬁc: Oxford, 1989; pp 469−474.

(

Kuwahara, Y. Conductivity Measurement of Polydiacetylene Thin

Films by Double-Tip Scanning Tunneling Microscopy. J. Phys. Chem.

B 2004, 108, 16353−16356.

H. Novel Polydiacetylenes for Optical Materials: Beyond the

Conventional Polydiacetylenes. J. Mater. Chem. 2000, 10, 819−828.

(

Okada, S. Solid-State Polymerization of a Pyrenylbutadiyne

Derivative. In Polymer Photonics and Novel Optical Technologies;

Kawabe, Y., Kawase, M., Eds.; Photonics World Consortium: Chitose,

47) Tatewaki, Y.; Shibata, H.; Shibuya, T.; Watanabe, K.; Ishii, S.;

(66) Jiang, H.; Hershtig, G.; Richter, S.; Jelinek, R. Light-Induced

Conductivity in a Solution-Processed Film of Polydiacetylene and

Perylene Diimide. J. Phys. Chem. Lett. 2016, 7, 1628−1631.

(67) Tang, Z.; Li, M.; Song, M.; Jiang, L.; Li, J.; He, Y.; Zhou, L.

48) Tatewaki, Y.; Sato, A.; Ito, S.; Inayama, S.; Okada, S. Synthesis

011; pp 152−155.

Good Conductivity of a Single Component Polydiacetylene Film. Org.

Electron. 2017, 49, 174−178.

and Solid-State Polymerization of L-Alanine Derivatives with a (1-

Pyrenyl)butadiynyl Group. Mol. Cryst. Liq. Cryst. 2013, 580, 58−63.

(

S.; Tokito, S. Synthesis and Solid-State Polymerization of Diacetylene

Derivatives with an N -Carbazolylphenyl Group. Bull. Chem. Soc. Jpn.

(68) Melby, L. R.; Harder, R. J.; Hertler, W. R.; Mahler, W.; Benson,

R. E.; Mochel, W. E. Substituted Quinodimethans. II. Anion-radical

Derivatives and Complexes of 7,7,8,8-Tetracyanoquinodimethan. J.

Am. Chem. Soc. 1962, 84, 3374−3387.

49) Ikeshima, M.; Mamada, M.; Katagiri, H.; Minami, T.; Okada,

(69) Prout, C. K.; Tickle, I. J.; Wright, J. D. Molecular Complexes.

XVI. Crystal Structure of the 1:1 Molecular Complex of Pyrene and

015, 88, 843−849.

50) Ikeshima, M.; Mamada, M.; Minami, T.; Tokito, S.; Okada, S.

Synthesis and Solid-State Polymerization of Diacetylene Derivatives

,7,8,8-Tetracyanoquinodimethane. J. Chem. Soc., Perkin Trans. 2

Directly Substituted by a Phenylcarbazole Moiety. Polym. J. 2016, 48,

973, 528−530.

70) Emge, T. J.; Maxfield, M.; Cowan, D. O.; Kistenmacher, T. J.

Solution and Solid State Studies of Tetrafluoro-7,7,8,8-Tetracyano-p -

013−1018.

51) Ishii, S.; Kaneko, S.; Tatewaki, Y.; Okada, S. Synthesis and

Quinodimethane, TCNQF . Evidence for Long-Range Amphoteric

Solid-State Polymerization of 4-(Dimethylamino)phenylbutadiyne

Derivatives and Their Charge-Transfer Complexes. Mol. Cryst. Liq.

Cryst. 2013, 580, 64−68.

Intermolecular Interactions and Low-Dimensionality in the Solid

State Structure. Mol. Cryst. Liq. Cryst. 1981 , 65 , 161 −178.

(71) Schofield, E.; Schulz, R. C. Synthesis and Complex Formation

of 1,6-Bis(3-pyrenyloxy)-2,4-hexadiyne. Makromol. Chem., Rapid

Commun. 1981, 2, 677−681.

(72) Dobrowolski, M. A.; Garbarino, G.; Mezouar, M.; Ciesielski, A.;

Cyranski, M. K. Structural Diversities of Charge Transfer Organic

Complexes. Focus on Benzenoid Hydrocarbons and 7,7,8,8-

Tetracyanoquinodimethane. CrystEngComm 2014, 16, 415−429.

(73) Sun, H.; Wang, M.; Wei, X.; Zhang, R.; Wang, S.; Khan, A.;

Usman, R.; Feng, Q.; Du, M.; Yu, F.; Zhang, W.; Xu, C.

Understanding Charge-Transfer Interaction Mode in Cocrystals and

Solvates of 1-Phenyl-3-(pyren-1-yl)prop-2-en-1-one and TCNQ.

Cryst. Growth Des. 2015, 15, 4032−4038.

52) Ikeshima, M.; Katagiri, H.; Fujiwara, W.; Tokito, S.; Okada, S.

Synthesis, Crystal Structures and Solid-State Polymerization of 8-[4-

Dimethylamino)phenyl]octa-5,7-diynyl Carbamates. Cryst. Growth

Des. 2018, 18, 5991−6000.

53) Imai, M.; Tatewaki, Y.; Okada, S. Preparation and Physical

Properties of Nanoaggregates Composed of Charge-Transfer

Complexes Containing Butadiyne Derivatives with Tetrathiafulvalene

Moieties. Jpn. J. Appl. Phys. 2014, 53, 05FA02.

Nakanishi, H.; Kato, M.; Kato, S. Solid-state Polymerization of 1,4-

54) Patel, G. N.; Chance, R. R.; Witt, J. D. A Visual Conformational

Transition in a Polymer Solution. J. Polym. Sci., Polym. Lett. Ed. 1978,

6, 607−614.

55) Sukwattanasinitt, M.; Lee, D.-C.; Kim, M.; Wang, X.; Li, L.;

(

(74) Tanaka, Y.; Iijima, S.; Shimizu, T.; Fujikawa, H.; Matsuda, H.;

Bis(3-acetylaminophenyl)-1,3-butadiyne under High Pressure. J.

Polym. Sci., Part C: Polym. Lett. 1986, 24, 177−184.

Yang, K.; Kumar, J.; Tripathy, S. K.; Sandman, D. J. New Processable,

Functionalizable Polydiacetylenes. Macromolecules 1999, 32, 7361−

369.

(

56) Takahashi, R.; Nunokawa, T.; Shibuya, T.; Tomita, R.;

Tatewaki, Y.; Okada, S.; Kimura, T.; Shimada, S.; Matsuda, H.

Synthesis and Solid-State Polymerization of Butadiyne Derivatives

with Trialkoxyphenylurethane Groups. Bull. Chem. Soc. Jpn. 2012, 85,

57) Kikuchi, K.; Tatewaki, Y.; Okada, S. Self-Assembly and Solid-

36−244.

State Polymerization of Butadiyne Derivatives with Amide and

Trialkoxyphenyl Groups. Bull. Chem. Soc. Jpn. 2017 , 90 , 298 −305.

58) Rubner, M. F. Synthesis and Characterization of Polyurethane-

Diacetylene Segmented Copolymers. Macromolecules 1986, 19, 2114−

128.

59) Beckham, H. W.; Rubner, M. F. Synthesis and Optical

Properties of a New Class of Polyamides Containing Reactive

Diacetylene Groups. Macromolecules 1989 , 22 , 2130 −2138.

60) Beckham, H. W.; Rubner, M. F. Structural Characterization of

the Cross-Polymerization of a Diacetylene-Functionalized Polyamide.

Macromolecules 1993, 26, 5192−5197.