3
48 Bull. Chem. Soc. Jpn., 78, No. 2 (2005)
Phenylethynylpyridinium for Nonlinear Optics
metric space group. A similar structural motif has been report-
ed for water containing crystals of 2e and its methoxy deriv-
ative.
By using the oriented-gas model,22 we estimated the d val-
ues of 1c and 1e compared with those of DAST. MO calcula-
Muramatsu, Japanese Patent Application 61-192404 (1986); S.
Okada, H. Matsuda, H. Nakanishi, M. Kato, R. Muramatsu,
Japanese Patent 1716929 (1992).
20
2
1
5
H. Nakanishi, H. Matsuda, S. Okada, and M. Kato, Mater.
Res. Soc. Int. Mtg. Adv. Mater., 1, 97 (1989).
S. R. Marder, J. W. Perry, and W. P. Schaefer, Science,
45, 626 (1989).
F. Pan, M. S. Wong, C. Bosshard, and P. G u¨ nter, Adv.
Mater., 8, 592 (1996).
6
tion results for the cation part in the crystal structures were
used for the ꢀ values. The ꢀ values of the cation part of 1c,
2
ꢃ30
7
1
e, and 2e were calculated to be 202 ꢂ 10
esu, 219 ꢂ
ꢃ30
ꢃ30
1
0
esu, and 255 ꢂ 10
esu, respectively. Also, the local
8 S. Sohma, H. Takahashi, T. Taniuchi, and H. Ito, Chem.
Phys., 245, 359 (1999).
9 M. Thakur, J. J. Xu, A. Bhowmik, and L. G. Zhou, Appl.
Phys. Lett., 74, 635 (1999).
field factors of 1c and 1e were set to be the same as those of
the 2e crystal at a wavelength of 1907 nm. The contribution
of the anion to the d values is negligible, because the ꢀ values
of these anions are only several percent of those of the counter
cations. As a result, the diagonal components of 1c and 1e
were calculated to be 51.6 and 65.0 pm/V, respectively, which
are one-fortieth to one-thirtieth of those of DAST (d11 ¼ 2010
pm/V). It is natural that the diagonal component decreased
when the angle ꢆ increase. On the other hand, the off-diagonal
components were estimated to be 257 and 288 pm/V, respec-
tively, which are more than twice those of DAST (d12 ¼ 124
pm/V). Also, these values are slightly larger than those of 1-
ethyl-4-{2-[4-(dimethylamino)phenyl]ethenyl}pyridinium p-
nitrobenzenesulfonate, studied previously.23 Large off-diago-
nal components are valuable for a wide range of applications,
like wavelength conversion, because the diagonal component
of the d values cannot be used due to a lack of the phase-
matching condition.
1
0
T. Kaino, B. Cai, and K. Takayama, Adv. Funct. Mater.,
2, 599 (2002).
F. Tsunesada, T. Iwai, T. Watanabe, H. Adachi, M.
Yoshimura, Y. Mori, and T. Sasaki, J. Cryst. Growth, 237, 2104
2002).
K. Nogi, Anwar, K. Tsuji, X.-M. Duan, S. Okada, H.
1
1
1
(
1
2
Oikawa, H. Matsuda, and H. Nakanishi, Nonlinear Opt., 24, 35
(2000).
13 H. Umezawa, K. Tsuji, Anwar, X.-M. Duan, S. Okada, H.
Oikawa, H. Matsuda, and H. Nakanishi, Nonlinear Opt., 24, 73
(2000).
14 S. Okada, K. Tsuji, Anwar, H. Nakanishi, H. Oikawa, and
H. Matsuda, Nonlinear Opt., 25, 45 (2000).
1
5
H. Umezawa, K. Tsuji, S. Okada, H. Oikawa, H. Matsuda,
and H. Nakanishi, Opt. Mater., 21, 75 (2002).
D. M. Burland, R. D. Miller, O. Reiser, R. J. Twieg, and C.
A. Walsh, J. Appl. Phys., 71, 410 (1992).
K. Kondo, N. Ohnishi, K. Takemoto, H. Yoshida, and K.
Yoshida, J. Org. Chem., 57, 1622 (1992).
H. Umezawa, S. Okada, H. Oikawa, H. Matsuda, and H.
Nakanishi, J. Phys. Org. Chem., in press.
S. Okada, A. Masaki, H. Matsuda, H. Nakanishi, M. Kato,
R. Muramatsu, and M. Otsuka, Jpn. J. Appl. Phys., 29, 1112
1990).
G. L. Bryant, Jr., C. P. Yakymyshyn, and K. R. Stewart,
Acta Crystallogr., C49, 350 (1993).
S. Okada, A. Masaki, K. Sakaki, T. Ohmi, T. Koike, E.
1
6
In conclusion, ethynyl analogue of DAST and its related
compounds with cation 1 were prepared and their properties
were investigated. All of the salts of cation 1 synthesized
1
7
(
1a–1f) were found to have noncentrosymmetric structures.
1
8
The crystal structures of 1c and 1e were analyzed to be isomor-
phous to each other, and were estimated to have a twice-larger
off-diagonal d component compared with that of DAST. These
crystals will be good candidates for second-order nonlinear
optical materials, especially wavelength conversion purposes.
1
9
(
2
0
2
1
References
Anzai, S. Umegaki, H. Matsuda, and H. Nakanishi, ‘‘Nonlinear
Optics—Foundamentals, Materials and Devices,’’ ed by S.
Miyata, Elsevier Science Publishers B. V., Amsterdam (1992),
p. 237.
22 J. Zyss and J. L. Ouder, Phys. Rev. A, 26, 2028 (1982).
23 S. Okada, K. Nogi, Anwar, K. Tsuji, X.-M. Duan, H.
Oikawa, H. Matsuda, and H. Nakanishi, Jpn. J. Appl. Phys., 42,
668 (2003).
1
2
S. R. Marder and J. W. Perry, Science, 263, 1706 (1994).
X.-M. Duan, H. Konami, S. Okada, H. Oikawa, H.
Matsuda, and H. Nakanishi, J. Phys. Chem., 100, 17780 (1996).
G. R. Meredith, ‘‘Nonlinear Optical Properties of Organic
3
and Polymeric Materials,’’ ACS Symp. Ser., 233, ed by D. J.
Williams, American Chemical Society, Washington, D.C.
(
1983), p. 27.
S. Okada, H. Matsuda, H. Nakanishi, M. Kato, R.
4