Single-crystal-to-single-crystal polymerization of 4,4′- butadiynedibenzylammonium disorbate

Article abstract of DOI:10.1246/cl.2004.1312

Solid-state polymerization of 4,4′-butadiynedibenzylammonium disorbate was investigated. The quantitative polymer yield of the diene moieties was achieved under UV-, X-ray, and γ-ray irradiation, whereas the conversion of diyne moieties was low. X-ray cry

Full text of DOI:10.1246/cl.2004.1312

1312
Chemistry Letters Vol.33, No.10 (2004)
Single-crystal-to-Single-crystal Polymerization of 4,40-Butadiynedibenzylammonium Disorbate
Toru Odani, Shuji Okada,y Chizuko Kabuto,yy Tatsumi Kimura,yyy Hiro Matsuda,yyy Akikazu Matsumoto,yyyy and Hachiro Nakanishi
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai 980-8577
yFaculty of Engineering, Yamagata University, Yonezawa, Yamagata 992-8510
yyGraduate School of Science, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578
yyyNational Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8565
yyyyGraduate School of Engineering, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585
(Received June 22, 2004; CL-040717)
Solid-state polymerization of 4,40-butadiynedibenzylammo-
I
a-c
d-f
nium disorbate was investigated. The quantitative polymer yield
of the diene moieties was achieved under UV-, X-ray, and ꢀ-ray
irradiation, whereas the conversion of diyne moieties was low.
X-ray crystal structure analyses of monomer and polymer crys-
tals show the polymerization proceeded under topochemical
polymerization mechanism indeed.
NH2
NHBoc
H3N
CO2
O2C
NH3
Topochemical polymerization in the crystalline state is one
of the most important methods in terms of the control of the re-
sulting polymer structure. By the topochemical polymerization,
we can obtain a stereoregular polymer as a crystal. Several poly-
merizable compounds in the crystalline state have been known
since late 1960s.1 Among them, the polymerization of diacety-
lene derivatives provides colored polymer based on their ꢁ-con-
jugated polymer backbone.2 In a recent decade, topochemical
polymerization of 1,3-diene derivatives such as sorbic and mu-
conic acid have been reported.3 The diene polymerization gives
colorless and non-conjugated polymer. The diene moieties in the
Scheme 1. Preparation of 4,40-butadiynedibenzylammonium
disorbate: (a) Boc2O in CHCl3, (b) TMS-acetylene,
Pd(PPh3)2Cl2, CuCl in triethylamine, (c) (n-Bu)4NF in THF,
(d) CuCl, TMEDA, O2 bubbling in acetone, (e) HCl aq/THF,
(f) sorbic acid in CHCl3.
after recrystallization from methanol for further experiments de-
scribed below. The polymerization also underwent by X-ray and
60Co ꢀ-ray irradiations. The maximum wavelength for the exi-
tonic band of the polydiacetylene was observed at 686 nm in dif-
fuse reflectance UV–vis spectrum as shown in Figure 1. CP/
MAS 13C NMR measurement was carried out to confirm the con-
version of each reaction group. After photoirradiation for 8 h, the
peak at 174.2 ppm assigned to the carbonyl carbon of the mono-
mer sorbate anions completely disappeared, and new carbonyl
peak was observed at 182.5 ppm. The peaks due to the methine
carbons were also appeared at 60.8 and 49.9 ppm. These results
show that the polymerization of the sorbate moieties underwent
almost quantitatively. On the other hand, the peaks at 80.7 and
74.2 ppm assigned to sp-carbons in the diyne moiety still re-
mained and peaks due to the polydiacetylene backbones were
too weak to be detected in the spectrum. Similar CP/MAS spec-
trum was obtained even after ꢀ-ray irradiation of 500 kGy dose.
The results indicate that the conversion of the diacetylene moie-
polymerizable crystals are oriented similarly to the fashion of di-
4
ꢀ
acetylene, i.e., aligned with a translation distance of 5 A. When
both of diyne and diene groups are incorporated in one system,
they are expected to be polymerized in a crystal. As a result, we
can obtain the highly regulated polymer network composed of
the diyne and diene polymers.5 The combination of carboxylic
acids and primary alkylamines were effective for the solid-state
polymerization of diacetylene6 and diene derivatives,7 respec-
tively. In this paper, we demonstrate the single-crystal-to-sin-
gle-crystal polymerization of 4,40-butadiynedibenzylammonium
disorbate. The molecular alignments of the monomer and poly-
mer are described. Especially, X-ray crystal structure analysis of
the polymer from ammonium salts of diene derivatives is the first
time to be reported.
4,40-Butadiynedibenzylammonium disorbate was prepared
as shown in Scheme 1. 4,40-Butadiynebenzylamine was synthe-
sized from 4-iodobenzylamine as a starting material. The ammo-
nium salt of sorbic acid was prepared by the reaction of sorbic
acid and diamine in chloroform as precipitant. Following recrys-
tallization from hot methanol gave plate crystals. Crystalline-
state polymerization of 4,40-butadiynedibenzylammonium disor-
bate was carried out under UV irradiation using high-pressure
mercury lamp attached a U340 filter at room temperature for
8 h. The recrystallized plate crystals became blue by UV irradi-
ation, indicating the formation of polydiacetylene. However, the
as-prepared powdery crystals were inert at the same condition.
The difference of reactivities is due to polymorph, which was
confirmed by powder X-ray diffraction. We used the monomer
350
450
550
650
750
850
Wavelength / nm
Figure 1. Diffuse reflectance UV–vis spectra of 4,40-butadiyne-
dibenzylammonium disorbate before and after polymerization.
Dotted line: monomer, solid line: after UV irradiation for 8 h.
Copyright Ó 2004 The Chemical Society of Japan

Chemistry Letters Vol.33, No.10 (2004)
1313
(a)
(b)
a
a
c
c
Figure 2. Crystal structure of 4,40-butadiynedibenzylammonium disorbate viewed from crystallographic b axis. (a) Monomer
recrystallized from methanol, (b) after X-ray irradiation for 48 h (Mo Kꢃ, 40 kV, 200 mA).
References and Notes
1
ties was low, although the exitonic band of polydiaetylene was
observed.
a) M. Hasegawa and Y. Suzuki, J. Polym. Sci., Part B:
Polym. Lett., 5, 813 (1967). b) G. Wegner, Z. Naturforsch.,
24B, 824 (1969). c) A. Matsumoto, T. Matsumura, and S.
Aoki, J. Chem. Soc., Chem. Commun., 1994, 1389. d) J.
Xiao, M. Yang, J. W. Lauher, and F. W. Fowler, Angew.
Chem., Int. Ed., 39, 2132 (2000). e) T. Ito, S. Nomura, T.
Uno, M. Kubo, K. Sada, and M. Miyata, Angew. Chem.,
Int. Ed., 41, 4306 (2002). f) T. Hoang, J. W. Lauher, and
F. W. Fowler, J. Am. Chem. Soc., 124, 10656 (2002).
V. Enkelmann, Adv. Polym. Sci., 63, 91 (1984).
Reviews: A. Matsumoto and T. Odani, Macromol. Rapid
Commun., 22, 1195 (2001); A. Matsumoto, Polym. J., 35,
93 (2003).
A. Matsumoto, K. Sada, K. Tashiro, M. Miyata, T.
Tsubouchi, T. Tanaka, T. Odani, S. Nagahama, T. Tanaka,
K. Inoue, S. Saragai, and S. Nakamoto, Angew. Chem., Int.
Ed., 41, 2502 (2002).
X-ray single-crystal analysis of the monomer was carried
out and result is shown in Figure 2a.8 The polymerization reac-
titvity of dienes was evaluated by the following four parameters
of the alignment of diene moieties proposed by Matsumoto et
al:4 the repeating distance along the polymerization direction
(ds), the distance between two carbons to make new bond during
polymerization (dcc), and the angles between the diene plane and
the polymerization direction (ꢂ1, ꢂ2). These parameters in the
monomer crystal are ds ¼ 4:88 A, dcc ¼ 5:38 A, ꢂ1 ¼ 26 , and
ꢂ2 ¼ 61ꢀ, respectively. These distances and angles are very sim-
ilar to those of the polymerizable crystals of alkylammonium
sorbates that have already been reported.7b Therefore, the diene
moieties polymerized smoothly in the crystalline state. On the
other hand, the diacetylene polymerization requires the molecu-
2
3
ꢀ
ꢀ
ꢀ
4
ꢀ
lar orientation with translation distance of 5 A and the angle of
45ꢀ between the translation axis and diyne moieties in the crys-
5
6
A. Matsumoto, D. Fujioka, and T. Kunisue, Polym. J., 35,
652 (2003).
talline state.2 For the present compound, the translation distance
ꢀ
was also 4.88 A, which was suitable for their polymerization in
a) H. Nakanishi, H. Matsuda, and M. Kato, Mater. Res. Soc.
Int. Mtg. Adv. Mater., 1, 291 (1989). b) K. Aoba, S. Okada,
S. Shimada, H. Matsuda, and H. Nakanishi, Mol. Cryst. Liq.
Cryst., 315, 59 (1998). c) A. Matsumoto, A. Matsumoto, T.
Kunisue, A. Tanaka, N. Tohnai, K. Sada, and M. Miyata,
Chem. Lett., 33, 96 (2004).
a) A. Matsumoto, T. Odani, M. Chikada, K. Sada, and M.
Miyata, J. Am. Chem. Soc., 121, 11122 (1999). b) S.
Nagahama, K. Inoue, K. Sada, M. Miyata, and A.
Matsumoto, Cryst. Growth Des., 3, 247 (2003).
the crystalline state. However, the tilt angle of the diyne moieties
against the translation axis was 60ꢀ, and the value is different
from the ideal angle 45ꢀ. It causes low conversion of the diyne
moieties.
We also succeeded the structure analysis of the polymer sin-
gle crystal that prepared by X-ray irradiation (40 kV, 200 mA,
48 h).8 The crystal structure after irradiation was solved as the
diene polymers with diyne monomers. The unit cell parameters
of these crystals were very similar, indicating that the polymer-
ization proceeded by the topochemical polymerization mecha-
nism indeed. The polymerization underwent along the crystallo-
graphic a axis, and the repeating distance of diene polymer
7
8
Crystal data for monomer: C15H16NO2, fw ¼ 242:29, triclin-
ꢁ
ꢀ
ic, space group P1, T ¼ 173 K, a ¼ 4:883ð3Þ A, b ¼
5:781ð3Þ A, c ¼ 22:520ð14Þ A, ꢃ ¼ 89:000ð14Þꢀ, ꢄ ¼
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ 3
89:011ð18Þ , ꢀ ¼ 84:398ð16Þ , V ¼ 632:5ð7Þ A , Z ¼ 2,
Dcalcd ¼ 1:272 g/cm3, Fð000Þ ¼ 258, ꢅðMo KꢃÞ ¼ 0:084
mmꢁ1. A total of 4481 reflections was measured, 2240 was
unique. 2129 (I > 2ꢆðIÞ) were used in the refinement of
163 parameters. R1 ¼ 0:045, wR2 ¼ 0:126, GOF ¼ 1:04.
For polymer: C15H16NO2, fw ¼ 242:29, triclinic, space
ꢀ
chains is 4.82 A, which is slightly shorter than the translation dis-
tance of the precursor monomers.
We demonstrated that the polymerization of 4,40-butadiyne-
dibenzylammonium disorbate proceeded under topochemical re-
action mechanism. With regard to ammonium salts of diene de-
rivatives, this is the first success of X-ray crystal structure analy-
sis of the polymer. Although the conversion of diyne moieties
was low, the polymer networks composed of two kinds of poly-
mer were partially formed. The conversion of diyne moieties
would be higher by the improvement of tilt angle.
ꢁ
ꢀ
ꢀ
group P1, T ¼ 293 K, a ¼ 4:818ð3Þ A, b ¼ 5:609ð2Þ A, c ¼
23:803ð10Þ A, ꢃ ¼ 89:02 (3)ꢀ, ꢄ ¼ 85:43ð4Þꢀ, ꢀ ¼
ꢀ
80:22ð4Þ , V ¼ 631:9ð5Þ A , Z ¼ 2, Dcalcd ¼ 1:273 g/cm3,
ꢀ
ꢀ 3
Fð000Þ ¼ 258, ꢅðMo KꢃÞ ¼ 0:085 mmꢁ1. 2917 reflections
was measured. 1456 (I > 2ꢆðIÞ) were used in the refinement
of 165 parameters. R1 ¼ 0:091, wR2 ¼ 0:256, GOF ¼ 1:06.
Crystallographic data reported in this manuscript have been
deposited with Cambridge Crystallographic Data Centre as
supplementary publication no. CCDC 248012 and 248013.
T. O. thanks for financial support by the research fellow-
ship of the Japan Society for the Promotion of Science for
young scientists.
Published on the web (Advance View) September 11, 2004; DOI 10.1246/cl.2004.1312