Solid-State Reactions of Crystals Containing Two ... - ACS Publications

May 12, 2009 - Hiro Matsuda,. ⊥. Hidetoshi Oikawa,† Akikazu Matsumoto,|| and Hachiro Nakanishi†. Institute of Multidisciplinary Research for AdV...
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CRYSTAL GROWTH & DESIGN

Solid-State Reactions of Crystals Containing Two Kinds of Polymerizable Moieties of Diene and Diyne

2009 VOL. 9, NO. 8 3481–3487

Toru Odani,† Shuji Okada,*,‡ Chizuko Kabuto,§ Tatsumi Kimura,⊥ Satoru Shimada,⊥ Hiro Matsuda,⊥ Hidetoshi Oikawa,† Akikazu Matsumoto,|| and Hachiro Nakanishi† Institute of Multidisciplinary Research for AdVanced Materials (IMRAM) and Graduate School of Science, Tohoku UniVersity, Sendai 980-8577, Japan, Graduate School of Science and Engineering, Yamagata UniVersity, Yonezawa 992-8510, Japan, National Institute of AdVanced Industrial Science and Technology (AIST), Tsukuba 305-8565, Japan, and Graduate School of Engineering, Osaka City UniVersity, Osaka 558-8585, Japan ReceiVed February 10, 2009; ReVised Manuscript ReceiVed April 27, 2009

ABSTRACT: We have investigated that photoreactivities of a series of diynediammonium dienecarboxylates in the crystalline state. In the case of 4,4′-butadiynedibenzylammonium disorbate, almost all diene moieties were polymerized during photoirradiation for 8 h. On the other hand, the conversion of diyne moieties was still low. Crystal structure of the monomer crystal indicates that the alignment of diene moieties is very similar to those of topochemically polymerizable crystals of diene derivatives. Even though the translation distance of diyne moieties is also suitable for the polymerization, the tilt angle is different from the ideal angle. It is the reason why the conversion of diyne moieties was low. By X-ray single-crystal structure analysis of the polymer crystal, we confirmed that the polymerization proceeded via topochemical reaction mechanism indeed. On the other hand, photodimerization of diene moieties in the crystals of 2,4-hexadiyne-1,6-diammonium (E,E)-muconate occurred because of the face-to-face alignment of dienes at a distance of 3.8 Å. 1. Introduction Reactions proceeding under the control of a crystal lattice have several advantages compared with the conventional reactions in solution.1 One of the biggest merits is that crystallinestate reactions give regio- and stereospecific products depending on the crystal structure of the reactant itself. However, the solidstate reaction is still limited because of the difficulty in controlling the crystal structure. Many researchers have been paid a great attention to control crystal structures using supramolecular interactions toward to the reactions in the crystalline state.2 Hydrogen bonding is well-known as typical supramolecular interactions, and many kinds of hydrogen-bond motifs in organic crystals have been reported.3 Topochemical polymerization in the crystalline state has been well-known since the discovery of diacetylenes4 (diyne) and distyrylpyradine5 derivatives in the 1960s. It is the most powerful polymerization method in terms of the controlling polymer structure. Not only stereochemistry of the polymer but also the molecular weight and their distribution can be controlled by controlling the crystal size and shape of monomers.6 Recently, new examples of topochemical polymerization were developed in addition to the traditional ones.7 Crystal engineering using supramolecular interactions has been reported to obtain a new polymer structure. Matsumoto et al. have reported the topochemical polymerization of diene derivatives such as muconic and sorbic acids.8 Four kinds of stereospecific polymers were provided depending on the crystal structures controlled by supramolecular interactions.9 The combination of carboxylic acids and primary alkylamines was effective for topochemical polymerizations of diene10 and diyne11 derivatives because of * Corresponding author. Phone and fax: 81-238-26-3741. E-mail: okadas@ yz.yamagata-u.ac.jp. † IMRAM, Tohoku University. ‡ Yamagata University. § Graduate School of Science, Tohoku University. ⊥ AIST. || Osaka City University.

the formation of two-dimensional hydrogen-bond networks. Especially the use of benzylammonium derivatives lead to achieve the proper alignment for the diene polymerization by the additional CH-π interaction between a hydrogen of methylene and a phenyl ring.10 The two-dimensional hydrogen-bond networks made the suitable 5 Å distance and alignment of the diene molecules for producing the polymer. This 5 Å requirement is very similar to that of the topochemical polymerization of diyne molecules reported by Enkelmann.12 In contrast to the formation of colorless and nonconjugated polymers obtained by the polymerization of diene derivatives, diyne derivatives give colored and π-conjugated polymers. They are promising materials for third-order nonlinear optics based on the π-electron delocalized polymer backbone.13 If both diyne and diene groups are incorporated in one system, they are expected to be polymerized in a crystal. As a result, the highly regulated polymer networks composed of the diyne and diene polymers may be obtained. In this paper, crystalline-state photoreaction of diynediammonium dienecarboxylates14 (1a-4d, Scheme 1) is described. We expected that the two benzylammonium groups directly attached to a diyne moiety 1a-4a could align dienecarboxylic acid moieties to suitable structure for polymerization by the formation of hydrogen-bond networks, and the diyne moieties themselves also could be polymerized. The direct connection of the diyne moiety to the phenyl rings of benzylammonium salts enhances the third-order nonlinear optical properties of their polymer because of the elongation of π-conjugation length.15 For comparison, diynediammonium dienecarboxylates without phenyl rings 1b-4b, those with one phenyl ring 1c-4c, and the isomers with two phenyl rings 1d-4d were also prepared, and the relation between crystal structures and photoreactivities is discussed. 2. Experimental Section Synthesis of Monomer Crystals. Synthesis of the diynediamines is described in the Supporting Information in detail. Monomer crystals were prepared by the reaction of the corresponding diynediamine and

10.1021/cg9001576 CCC: $40.75  2009 American Chemical Society Published on Web 05/12/2009

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Scheme 1. Chemical Structures of Dienecarboxylic Acid and Diynediamime Used in This Study

dienecarboxylic acid in chloroform or methanol. The precipitants were filtrated and dried in a vacuum. In the case of disorbate, the crystals were purified by the recrystallization from hot methanol or water. Muconate crystals were used for the reaction without further purification. 4,4′-Butadiynylenedibenzylammonium Disorbate (1a). 1H NMR (400 MHz, CD3OD) δ 7.57 (d, J ) 8.4 Hz, 4H, Ar), 7.44 (d, J ) 8.4 Hz, 4H, Ar), 7.03 (m, 2H, )CH), 6.20 (m, 2H, )CH), 6.05 (m, 2H, )CH), 5.78 (d, J ) 14.9 Hz, 2H, )CH), 4.04 (s, 4H, CH2), 1.83 (d, J ) 6.5 Hz, 6H, CH3); CP/MAS 13C NMR (75 MHz) δ 174.1, 140-125, 120.5, 80.7, 74.5, 20.5; IR (cm-1) 1624 (νCdC), 1508 (νCOO-). 4,4′-Butadiynylenedibenzylammonium (Z,Z)-Muconate (2a). 1H NMR (400 MHz, D2O) δ 7.51 (d, J ) 8.3 Hz, 4H, Ar), 7.32 (d, J ) 8.3 Hz, 4H, Ar), 6.78 (m, 2H, )CH), 5.80 (m, 2H, )CH), 4.06 (s, 4H, CH2); CP/MAS 13C NMR (75 MHz) δ 175.2, 140-125, 120.4, 80.7, 74.7, 28.9; IR (cm-1) 1587 (νCdC), 1508 (νCOO-). 4,4′-Butadiynylenedibenzylammonium (E,Z)-Muconate (3a). 1H NMR (400 MHz, D2O) δ 7.51 (d, J ) 7.7 Hz, 4H, Ar), 7.44 (m, 1H, )CH), 7.31 (d, J ) 7.7 Hz, 4H, Ar), 6.25 (m, 1H, )CH), 5.88 (m, 2H, )CH), 4.06 (s, 4H, CH2); IR (cm-1) 1604 (νCdC), 1500 (νCOO-). 4,4′-Butadiynylenedibenzylammonium (E,E)-Muconate (4a). 1H NMR (400 MHz, D2O) δ 7.51 (d, J ) 8.0 Hz, 4H, Ar), 7.32 (d, J ) 8.0 Hz, 4H, Ar), 6.93 (m, 2H, )CH), 6.05 (m, 2H, )CH), 4.06 (s, 4H, CH2); IR (cm-1) 1616 (νCdC), 1512 (νCOO-). 2,4-Hexadiyne-1,6-diammonium Disorbate (1b). 1H NMR (400 MHz, CD3OD) δ 7.09 (dd, J ) 15.4 and 10.8 Hz, 2H, )CH), 6.20 (m, 2H, )CH), 6.07 (m, 2H, )CH), 5.77 (d, J ) 15.4 Hz, 2H, )CH), 3.69 (s, 4H, CH2), 1.82 (d, J ) 6.4 Hz, 6H, CH3); 13C NMR (100 MHz, CD3OD) δ 174.1, 143.7, 137.9, 131.5, 124.5, 75.5, 69.6, 30.9, 18.6; IR (cm-1) 1625 (νCdC), 1506 (νCOO-). 2,4-Hexadiyne-1,6-diammonium (Z,Z)-Muconate (2b). 1H NMR (400 MHz, D2O) δ 6.81 (m, 2H, )CH), 5.81 (m, 2H, )CH), 3.80 (s, 4H, CH2); 13C NMR (100 MHz, D2O) δ 176.3, 131.5, 130.1, 71.9, 70.6, 30.4; IR (cm-1) 1581 (νCdC), 1524 (νCOO-). 2,4-Hexadiyne-1,6-diammonium (E,Z)-Muconate (3b). 1H NMR (400 MHz, D2O) δ 7.45 (m, 1H, )CH), 6.26 (m, 1H, )CH), 5.88 (m, 2H, )CH), 3.80 (s, 4H, CH2); 13C NMR (100 MHz, D2O) δ 176.2, 176.0, 137.2, 134.4, 132.1, 131.7, 71.9, 70.6, 30.3; IR (cm-1) 1603 (νCdC), 1533 (νCOO-). 2,4-Hexadiyne-1,6-diammonium (E,E)-Muconate (4b). 1H NMR (400 MHz, D2O) δ 6.87 (m, 2H, )CH), 6.03 (m, 2H, )CH), 3.79 (s, 4H, CH2); IR (cm-1) 1615 (νCdC), 1519 (νCOO-). 5-[4-(Ammoniomethyl)phenyl]-2,4-pentadiynylammonium Disorbate (1c). 1H NMR (400 MHz, CD3OD) δ 7.55 (d, J ) 8.6 Hz, 2H, Ar), 7.44 (d, J ) 8.6 Hz, 2H, Ar), 7.07 (dd, J ) 15.3 and 10.7 Hz, 2H, )CH), 6.20 (m, 2H, )CH), 6.05 (m, 2H, )CH), 5.78 (d, J ) 15.3 Hz, 2H, )CH), 4.09 (s, 2H, CH2), 3.67 (s, 2H, CH2), 1.82 (d, J ) 6.6 Hz, 6H, CH3); CP/MAS 13C NMR (75 MHz) δ 175.7, 140-125, 119.3, 77.9, 72.0, 68.8, 59.6, 21.0; IR (cm-1) 1630 (νCdC), 1508 (νCOO-). 5-[4-(Ammoniomethyl)phenyl]-2,4-pentadiynylammonium (Z,Z)Muconate (2c). 1H NMR (400 MHz, D2O) δ 7.47 (d, J ) 8.1 Hz, 2H, Ar), 7.29 (d, J ) 8.1 Hz, 2H, Ar), 6.81 (m, 2H, )CH), 5.80 (m, 2H, )CH), 4.04 (s, 2H, CH2), 3.86 (s, 2H, CH2); IR (cm-1) 1585 (νCdC), 1509 (νCOO-). 5-[4-(Ammoniomethyl)phenyl]-2,4-pentadiynylammonium (E,Z)Muconate (3c). 1H NMR (400 MHz, D2O) δ 7.45 (d, J ) 8.6 Hz, 2H, Ar), 7.40 (m, 1H, )CH), 7.27 (d, J ) 8.2 Hz, 2H, Ar), 6.23 (m, 1H, )CH), 5.86 (m, 2H, )CH), 4.04 (s, 2H, CH2) 3.86 (s, 2H, CH2); IR (cm-1) 1604 (νCdC), 1510 (νCOO-).

5-[4-(Ammoniomethyl)phenyl]-2,4-pentadiynylammonium (E,E)Muconate (4c). 1H NMR (400 MHz, D2O) δ 7.45 (d, J ) 8.3 Hz, 2H, Ar), 7.27 (d, J ) 8.3 Hz, 2H, Ar), 6.83 (m, 2H, )CH), 5.98 (m, 2H, )CH), 4.02 (s, 2H, CH2), 3.85 (s, 2H, CH2); IR (cm-1) 1620 (νCdC), 1510 (νCOO-). 3,3′-Butadiynylenedibenzylammonium Disorbate (1d). 1H NMR (400 MHz, D2O) δ 7.50 (m, 4H, Ar), 7.35 (m, 4H, Ar), 6.97 (m, 2H, )CH), 6.08 (m, 4H, )CH), 5.65 (d, J ) 15.4 Hz, 2H, )CH), 4.04 (s, 4H, CH2), 1.66 (d, J ) 6.1 Hz, 6H, CH3); IR (cm-1) 1611 (νCdC), 1506 (νCOO-). 3,3′-Butadiynylenedibenzylammonium (E,Z)-Muconate (3d). 1H NMR (400 MHz, D2O) δ 7.50 (m, 42H, Ar), 7.45 (m, 1H, )CH), 7.35 (m, 4H, Ar), 6.26 (m, 1H, )CH), 5.88 (m, 2H, )CH), 4.04 (s, 4H, CH2); IR (cm-1) 1594 (νCdC), 1512 (νCOO-). 3,3′-Butadiynylenedibenzylammonium (E,E)-Muconate (4d). 1H NMR (400 MHz, D2O) δ 7.49 (m, 4H, Ar), 7.35 (m, 4H, Ar), 6.86 (m, 2H, )CH), 6.01 (m, 2H, )CH), 4.04 (s, 4H, CH2); IR (cm-1) 1614 (νCdC), 1526 (νCOO-). Poly(1a). CP/MAS 13C NMR (75 MHz) δ 182.5, 140-125, 120.4, 80.7, 74.2, 60.9, 42.9, 22.0; IR (cm-1) 1541 (νCOO-). Poly(2a). CP/MAS 13C NMR (75 MHz) δ 181.2, 140-125, 120.5, 80.7, 74.3, 59.6, 45.7; IR (cm-1) 1541 (νCOO-). Poly(1c). CP/MAS 13C NMR (75 MHz) δ 182.9, 140-125, 119.6, 78.1, 72.7, 69.3, 59.9, 43.0, 21.9; IR (cm-1) 1540 (νCOO-). Solid-State Reactions. Photoirradiation was carried out using a 500 W ultrahigh-pressure mercury lamp (Ushio through a U 340 filter) at ambient temperature. For γ-ray-induced polymerization, the samples were charged into Pyrex tubes, degassed, and sealed. Irradiation was carried out with 60Co. Measurements. IR spectra were recorded by the ATR mode on a Nicolet A360 spectrometer with a DuraScope attachment (SensIR Technologies). UV-visible spectra were taken with a JASCO V-570 spectrometer. NMR spectra in solution were measured by a JEOL JMNLA 400 spectrometer. Solid-state 13C NMR spectra were recorded using the cross-polarization/magic angle spinning (CP/MAS) method on a Bruker MSL-300 spectrometer referring the methylene carbon peak of adamantane at 29.5 ppm as an external standard. Powder X-ray diffraction profiles were taken with a Mac Science M19XHF22-SRA diffractometer with Cu KR radiation. X-ray single-crystal structure analyses were carried out with a Mac Science M03XHF22-SRA diffractometer or a Rigaku Mercury system attached a CCD area detector using Mo KR radiation.

3. Results and Discussion Photoreaction. Table 1 shows the results of the photopolymerization of ammonium salts during UV irradiation for 8 h. The crystals of 1a, 1c, and 2a became blue during UV irradiation (Figure 1 for 1a as an example). In the IR spectra of the crystals, the peak corresponding to the diene moieties disappeared during the irradiation. The sharp peaks were observed in powder X-ray diffraction profiles of 1a, 1c, and 2a even after the polymerization (see the Supporting Information). These results indicate that the crystals were polymerized and the crystalline state was maintained during the polymerization. As we expected, the crystals of monomers having 4-substituted benzylammonium

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Table 1. Photoreaction of Diynediammonium Dienecarboxylates under UV Irradiation for 8 h compd

photoproduct (yield (%))

1a 1b 1c 1d 2a 2b 2c 2d 3a 3b 3c 3d 4a 4b 4c 4d

polymer (92a) none polymer (91a) none polymer (64a) (E,E)-diene by isomerization (6b>) none none none (E,E)-diene by isomerization (33b) none none none dimerized compound of dienes none none

Figure 2. UV-vis diffuse reflectance spectra of 1a crystals. Dotted line is for monomer and solid line is for 1a after photoirradiation for 8 h.

a Polymerization yield was determined gravimetrically after extracting unreacted monomer. Polymer color was all blue. b Isomerization conversion was determined by 1H NMR.

Figure 3. CP/MAS 13C NMR spectra of (a) 1a monomer, (b) 1a after photoirradiation for 8 h, and (c) 1a after 1.5 MGy of γ-ray radiation.

Figure 1. Photographs of 1a crystals: (a) before and (b) after photoirradiation.

groups tend to polymerize in the crystalline state. On the other hand, 3,3′-butadiynylenedibenzylammonium and hexadiynediammonium salts did not provide any polymers, and no reaction proceeded. Reactions other than solid-state polymerization were observed for the following compounds. For hexadiynediammonium salts of (Z,Z)- and (E,Z)-muconic acids (2b and 3b), isomerization of diene moieties to the (E,E)-isomer occurred in the crystalline state.16 For 4b, dimerization of (E,E)-muconate proceeded in the crystalline state. Polymerization. Among the polymerizable crystals, polymerization of 1a was investigated in detail. UV-vis spectra of the 1a crystals before and after UV irradiation are shown in Figure 2. The color of the crystals was changed to blue during photoirradiation. This result indicates the formation of polydiacetylene. The maximum wavelength for the excitonic band of the polydiacetylene was observed at 686 nm in the diffuse reflectance spectrum. This wavelength is shifted to longer wavelength compared with the conventional polydiacetylenes, indicating π-conjugation extension due to the conjugation effect

of phenyl rings directly bound to the polymer backbone in 1a. CP/MAS 13C NMR measurement was carried out to confirm the conversion to the polymer in each reaction groups as shown in Figure 3. In the spectrum after photoirradiation for 8 h (Figure 3b), new peaks e′ and b′ due to the methine carbons appeared at 61 and 43 ppm, respectively. In addition, peak f at 174 ppm in Figure 3 (a) assigned to the carbonyl carbon of the monomer sorbate anions completely disappeared, and new carbonyl peak f′ in Figure 3 (b) was observed at 182 ppm. These results show that the polymerization of the sorbate moieties occurs almost quantitatively. On the other hand, the peaks at 81 and 74 ppm assigned to sp-carbons in the diyne moiety still remained in Figure 3 (b) and peaks due to the polydiacetylene backbones were too weak to be detected in the spectrum. Similarly to 1a, 2a and 1c were polymerized only in the diene moieties with high conversions after photoirradiation. Even in the case of asymmetrical compound 1c, photopolymerization of the diene moieties of both sorbate anions was confirmed by the CP/MAS spectrum (see the Supporting Information). Since the low conversion of diyne moieties by photopolymerization was found in spite of the crystal color change to blue, other polymerization methods were carried out to achieve the higher conversion of the diyne moieties to give the polymers. First, γ-ray irradiation was used because it can penetrate into colorized crystals. After 60Co γ-ray radiation, the crystals also became blue, indicating that the polymerization of the diyne moieties occurred. CP/MAS NMR spectrum of 1a after 500 kGy of radiation was similar to that obtained after UV irradiation

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Figure 4. Crystal structure of 1a: (a) view along the b axis, (b) alignment of sorbate anions, and (c) alignment of diynediammonium moieties. Figure 6. Crystal structure of 1b: (a) view along the a axis and (b) alignment of sorbate anions.

Figure 5. Crystal structure of poly(1a) viewed along the b axis.

for 8 h. The peaks due to the diyne moieties still remained strong and a new peak due to the acetylenic carbon of the polymer backbone, which was expected to be observed between 100 and 110 ppm, was too weak to be detected in the spectrum. The high conversion of the diyne moieties was not achieved even after 1.5 MGy of γ-ray radiation as shown in Figure 3c. On the other hand, the conversion of the diene moieties increased by increasing the radiation dose. Next, thermal polymerization of 1a monomer was carried out at 140 °C for 8 h. Although its polymerization also occurred by heating, the color of the crystals after heating was pale blue. CP/MAS NMR spectrum showed that in addition to almost no conversion of the diyne moieties, the conversion of diene moieties was also low compared with the case of photopolymerization (see the Supporting Information). Instead of monomer crystals, thermal treatment of diyne moieties in the dienepolymer crystals prepared by γ-ray polymerization was carried out to increase the conversion of the diyne moieties because the polymer crystals are thermally much more stable than monomer crystals. The polymer crystals were heated under an argon flow at 240 °C for 8 h. However, CP/MAS spectrum after the thermal treatment was very similar to the spectrum before heating. The conversion of diyne moieties of these crystals was not improved even after a large amount of γ-ray radiation followed by thermal treatment.

Figure 7. Crystal structure of 4b: (a) view along the a axis and (b) alignment of muconate anions.

Crystal structure of 1a is shown in Figure 4. The polymerization reactivity of dienes was evaluated by the following four parameters related to the alignment of diene moieties proposed by Matsumoto et al.: the repeating distance along the polymerization direction (ds), the distance between two carbons to make a new bond during polymerization (dcc), and the angles between the diene plane and the polymerization direction (θ1 and θ2). These parameters in the monomer crystal are ds ) 4.88 Å, dcc ) 5.38 Å, θ1 ) 26°, and θ2 ) 61°, respectively. These

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Figure 8. 1H NMR Spectrum of 4b in D2O after photoirradiation for 8 h.

Scheme 2. Reaction Scheme of (E,E)-Muconate in Crystals of 4b

distances and angles are very similar to those of the polymerizable crystals of alkylammonium sorbates that have already been reported.8 Therefore, the diene moieties polymerized smoothly in the crystalline state. On the other hand, the polymerization of diyne compounds requires the molecular orientation with translation distance of about 5 Å and the angle of about 45° between the translation axis and diyne moieties in the crystalline state.12 For the present compound, the translation distance is also 4.88 Å, which is a suitable for their polymerization in the crystalline state. However, the tilt angle of the diyne moieties against the translation axis is 60°, and this value is different from the ideal angle of 45°. The deviation from the ideal tilt angle causes low conversion of the diyne moieties. We also succeeded in analyzing the structure of a poly(1a) single crystal prepared by long-time X-ray radiation (Cu KR,

Figure 9. Hydrogen-bonding motifs of (a) 1a, (b) 1b, and (c) 4b.

40 kV, 200 mA, 48 h) as shown in Figure 5. The crystal structure after radiation was solved as the diene polymers with diyne monomers. This crystal structure is consistent with the result of CP/MAS 13C NMR measurements. The unit cell parameters of the polymer crystal were very similar to those of the crystal before irradiation, i.e., the polymerization occurred by the topochemical polymerization mechanism indeed. The polymerization proceeded along the crystallographic a axis, and the repeating distance of diene polymer chains is 4.82 Å, which is slightly shorter than the translation distance of the precursor monomers. Figure 6 shows the crystal structure of 1b that did not provide any photoproducts. The diene and diyne molecules formed a layered structure similar to that of the polymerizable crystals. However, the molecules were shifted alternately, and the

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distance between molecules along the possible polymerization direction was too short for the topochemical polymerization. Even though the distance between two diene molecules was close for photodimerization, they do not react under UV irradiation because the diene molecules alternately pile up in the flat and tilted manner along the crystallographic b axis. Dimerization. Dimerization reaction of 4b proceeded during UV irradiation for 8 h. Figure 7 shows the crystal structure of 4b before UV irradiation. The diene moieties aligned face-toface manner with a distance of 3.8 Å between the nearest diene carbons of the adjacent muconates. The distances meet Schmidt’s rule for the dimerization in the crystalline state17 and this crystal structure was suitable for the dimerization in the crystalline state. 1 H NMR spectrum of the photoproducts was able to be assigned as two dimers as shown in Figure 8. Cyclooctadiene dimer 6 was mainly observed and small amount of [2 + 2] cyclobutane dimer 5 was also observed. It is assumed that the [2 + 2] dimer was formed by the crystalline-state photoreaction of a pair of double bonds, and then, the dimer would be thermally isomerized to the cyclooctadiene dimer as shown in Scheme 2. Actually, the solution sample was heated before 1H NMR measurement to solve the monomer and photoproducts, and this may cause that most of the products were transformed to the cyclooctadiene dimer via Cope rearrangement. This reaction mechanism of muconic acid derivatives was already reported by Green et al.18 The conversion of muconate could not be estimated by 1H NMR because the crystals did not solve perfectly. Recently, Gao et al. have reported the synthesis of ladderane in the crystalline state using hydrogen bonding between pyridine and resorcinol.19 The 4b crystals seems to be possible to form ladderane by stepwise [2 + 2] dimerization. However, no evidence suggesting the formation of ladderane was obtained in this case. Hydrogen Bonding. Carboxylates and primary amines in the crystals form hydrogen-bond networks. They act as a triple donor and a triple acceptor, respectively. Figure 9 shows the hydrogen-bond networks of 1a, 1b, and 4b in the crystals. A two-dimensional hydrogen-bond network, which is often observed in the polymerizable crystals of diene monomers, is formed in 1a crystals. The hydrogen bonding is aligned perpendicular to the polymerization direction. The hydrogenbond network leads to the suitable orientation and direction of diene molecules for topochemical polymerization. Another type of two-dimensional hydrogen-bond network was observed in 1b crystals. This network is formed by rings consists of 16 atoms. This atom number is the same as that for the network of 1a crystals. However, there are two types of 16-membered rings in 1b crystals while only one type of 16-membered rings are repeated in 1a crystals. As a result, the distance of translational carboxylate in 1b crystals was too far for the polymerization, i.e., 8.05 Å as shown in Figure 6. In the case of 4b crystals, a one-dimensional ladder-type network consisted of 8- and 12membered rings was observed, and it is one of typical patterns of hydrogen bonding between carboxylates and primary amines.3j,10d 4. Conclusion We prepared the crystals having both diene and diyne moieties in a crystal and demonstrated the crystalline-state reactions. Polymerization or dimerization proceeded depending on the crystal structure of the reactants. The combination of benzylammonium salt and carboxylic acids formed suitable crystal structure for both reacting group by the formation of two-dimensional hydrogen-bond network, and the polymer

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crystals composed by two kinds of polymer was obtained via the topochemical polymerization mechanism. The diene moieties were polymerized quantitatively during photo- or γ-ray radiations. However, it is very difficult to obtain the high conversion of diynes in these polymerizable crystals. To achieve the high conversion, the tilt angle of diyne moieties must be controlled around 45° in the crystalline state. On the other hand, photodimerization of diene moieties in the crystals of 4b proceeded because the face-to-face alignment of dienes at a distance of 3.8 Å satisfied Schmidt’s rule for [2 + 2] dimerization. Acknowledgment. T.O. thanks for financial support by the research fellowship of the Japan Society for the Promotion of Science for young scientists. Supporting Information Available: Synthesis procedures, X-ray diffractograms, and 13C NMR spectra (PDF); crystallographic information files (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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