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