Synthesis of azo chromophores containing a perfluorocyclo-alkenyl moiety and their second-order optical nonlinearity

Article abstract of DOI:10.1016/S0022-1139(99)00050-0

1,2-Bis[4-[4-[N-ethyl-N-(2-hydroxyethyl)amino]phenylazo]phenylthio] perfluorocyclopentene, having two independent intramolecular push-pull chromophores in a molecule, showed the highest second-order nonlinear coefficient (d₃₃) among the cyclobutenyl, -pentenyl, -hexenyl, and cyclopentenyl nitro derivatives in both doped poly(methyl methacrylate) (PMMA) and polycarbonate (PC).

Full text of DOI:10.1016/S0022-1139(99)00050-0

Journal of Fluorine Chemistry 97 (1999) 207±212
Synthesis of azo chromophores containing a per¯uorocyclo-alkenyl
moiety and their second-order optical nonlinearity
Masaki Matsuia,*, Michinori Tsugea, Kazumasa Funabikia, Katsuyoshi Shibataa,
Hiroshige Muramatsua, Kazuo Hirotab, Masahiro Hosodab, Kazuo Taib,
Hisayoshi Shiozakic, Misa Kimd, Kazumi Nakatsud
aDepartment of Chemistry, Faculty of Engineering, Gifu University, Yanagido 501-1193 Gifu, Japan
bResearch and Development Center, Unitika Ltd., Kozakura 23, Uji 611-0021 Kyoto, Japan
cTechnology Research Institute of Osaka Prefecture, Kishibenaka 1-18-13, 564-0002 Suita, Japan
dSchool of Science, Kwansei Gakuin University, Uegahara 1-1-155, 662-8501 Nishinomiya, Japan
Received 8 December 1998; received in revised form 23 January 1999; accepted 25 January 1999
Dedicated to the 75th birthday of Prof. Yoshiro Kobayashi
Abstract
1,2-Bis[4-[4-[N-ethyl-N-(2-hydroxyethyl)amino]phenylazo]phenylthio]per¯uorocyclopentene, having two independent intramolecular
push-pull chromophores in a molecule, showed the highest second-order nonlinear coef®cient (d33) among the cyclobutenyl, -pentenyl,
-hexenyl, and cyclopentenyl nitro derivatives in both doped poly(methyl methacrylate) (PMMA) and polycarbonate (PC). # 1999 Elsevier
Science S.A. All rights reserved.
Keywords: Second-order optical nonlinearity; Per¯uorocycloalkenyl; Azo dyes
1. Introduction
2. Results and discussion
Much attention has been paid to prepare nonlinear optical
chromophores (NLOphores) having large second-order non-
linearity. To design the NLOphores, ꢀ-conjugated com-
pounds possessing large dipole moment, bathochromicity,
and intense absorptivity (molar absorption coef®cient (ꢁ))
are required [1]. Many compounds such as Disperse Red 1
(4-(4-nitrophenylazo)-N-ethyl-N-(2-hydroxyethyl)aniline,
DR1) [2], 4-(dimethylamino)-40-nitrostylbene (DANS) [3],
disazo dyes [4±7], cyanine dyes [8±11], benzopyrilium salts
[12] and azomethine dyes [13] being largely dipolar and
bathochromic compounds, have been proposed as excellent
NLOphores. However, little attention has been paid to
prepare the compounds having intense ꢁ values. When a
NLOphore consists of independent chromophores, an
intense ꢁ value of the compounds is expected. In this paper,
we report the synthesis of azo chromophores linked with the
per¯uorocycloalkenyl moiety and their second-order optical
nonlinearities.
Scheme 1 shows the synthesis of NLOphores 3a±c and 5b.
The NLOphores 3a±c were prepared by the reaction of 1,2-
dichloroper¯uorocycloalkenes with 4-aminothiophenol in
the presence of sodium hydride to give dianilino intermedi-
ates 2a±c, followed by diazotization-coupling reaction. The
nitro derivative 5b was obtained by way of monoanilino
intermediate 4b.
Since little is known about the electronic effect of per-
¯uorocyclopentenylthio moiety, intramolecular push±pull
chromophoric azobenzene derivatives were prepared. Their
absorption maxima were plotted against Hammett's ꢂp
constants. The result is shown in Fig. 1. The per¯uoro-
cyclopentenylthio substituent showed similar electron-with-
drawing nature to a tri¯uoromethyl group (ꢂp: 0.54).
The molecular structure of 3b is shown in Fig. 2. Crystal-
lographic data and selected bond lengths and various angles
are given in Tables 1 and 2, respectively. The molecule was
V-shaped: two long azo chromophores protruded from
roughly planar cyclopentene (CP) ring via the sulfur atoms
S1 and S2. The conformations around S1 and S2 were
different each other: C2±C1±S1±C7 linkage was assumed
*Corresponding author. Tel.: +81-58-230-2601; fax: +81-58-230-1893;
e-mail: matsui@apchem.gifu-u.ac.jp
0022-1139/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 0 5 0 - 0

208
M. Matsui et al. / Journal of Fluorine Chemistry 97 (1999) 207±212
Scheme 1. Synthesis of NLO phores.
trans, while that of C1±C2±S2±C27 nearly gauche. Both azo
groups, Azo1 and Azo2, took trans con®guration. Two
phenyl groups bonded to the azo groups were twisted in
opposite direction each other: 7.2 and 8.28 in Azo1 and 16.8
and 19.78 in Azo2. All the bond lengths and angles were in
the range of empirical values, except a few bond lengths.
Ê
The C±N distances of 1.51±1.55 A were longer than the
Ê
generally accepted value of 1.43±1.46 A. The S±C(CP)
Ê
bonds of 1.733 and 1.757 A were somewhat shorter than
Ê
the S±C(Ph) bonds of 1.783(7) and 1.783(8) A, indicating
and 5b (442 and 351 nm) were more hypsochromic than DR
1 (482 nm), due to the less electron-withdrawing nature of
per¯uorocycloalkenylthio moieties than the nitro group. As
expected, NLOphores 3a±c showed more intense ꢁ value
(46 000±77 000 in ethanol) than DR 1 (27000). The decom-
position temperature (Td) of 3b was observed to be 2908C
by TG-DTA analysis, indicating that these compounds were
stable enough under poling conditions. Interestingly, these
NLOphores were soluble in organic solvents such as etha-
nol, acetone, and chloroform.
slight differences of double-bond character for the bonds.
The van der Waals interaction was dominant among the
molecules, except that two hydrogen bonds were formed to
A dichloromethane solution of the polymer matrix con-
taining the NLOphores was put on an ITO glass, spin-
coated, dried, and corona-poled at the transition temperature
of the polymers. The second-harmonic generation (SHG) of
the ®lm was measured by the Maker fringe method using a
Q-switched Nd:YAG laser (ꢃˆ1064 nm). The second-order
NLO coef®cient (d33) was then determined by the mean
square methods using the relationship of the second har-
monic light intensity and the incident angle of the poled
®lm. The d33 values of 3a±c and 5b in doped PMMA and PC
are also shown in Table 3. The hypsochromic NLOphores
3a±c showed higher second-order nonlinearity than DR 1,
Ê
link the molecules: O11±H±O21ˆ2.72(1) A and O21±H±
Ê
N21ˆ2.90(1) A.
The physical data of NLOphores are summarized in
Table 3. NLOphores 3a±c (ꢃmax; 438±441 nm in EtOH)
Table 1
Crystallographic data for 3b
Formula
C37H36F6N6O2S
Mol. wt
774.12
Red, Plate-like
Crystal color, habit
Crystal system
Space group
Unit cell dimensionsa
Triclinic
ꢀ
P 1
Ê
Ê
aˆ14.631(3) A
bˆ17.667(5) A
ꢄˆ99.36(4)
ꢆˆ79.72(4)
Ê
cˆ7.586(7) A
ꢅˆ99.51(4)
Ê 3
Vˆ1884(2) A
a
Fig. 1. Hammett's plot for the absorption maxima of azobenzenes. The
a Throughout this paper the standard deviation in the least significant digit
of the proceeding value is given in parenthesis.
absorption bands were measured in hexane.

M. Matsui et al. / Journal of Fluorine Chemistry 97 (1999) 207±212
209
Fig. 2. Perspective drawing of the molecular structure of 3b (the carbon atoms are shown only by numbers)
due to their intense ꢁ values. The NLOphore 3b also showed
3.1. Synthesis of 5-acetyl-4-arylazo-2-methoxy-N,N-
diethylanilines
larger d33 value than the nitro derivative 5b. The NLOphore
3b showed the largest d33 value among 3a±c and 5b.
In conclusion, azo NLOphores containing a per¯uoro-
cycloalkenyl moiety have been synthesized. The second-
order nonlinearity of 1,2-bis[4-[4-[N-ethyl-N-(2-hydroxyethyl)-
amino]phenylazo]phenylthio]per¯uorocyclopentene
showed the highest d33 value among four-, ®ve-, and six-
membered symmetrical and ®ve-membered nitro deriva-
tives.
To an acetone±water mixed solution (1:1, 20 ml) of conc.
hydrochloric acid (1.35 ml, 15.1 mmol) was added an ani-
line (5.4 mmol). The mixture was stirred for 1 h at room
temperature and cooled to 08C. To the mixture was added an
aqueous solution (10 ml) of sodium nitrite (5.5 mmol) and
the mixture was stirred for 30 min at 08C. To the mixture
was added an acetone solution (15 ml) of 5-acetylamino-2-
methoxy-N,N-diethylaniline (1.3 g, 5.5 mmol) and the mix-
ture was stirred for 1 h. The pH value of the solution was
adjusted to 7.0 with an aqueous sodium hydroxide solution.
The resulting precipitate was ®ltered, puri®ed by column
chromatography (SiO2, CH2Cl2), and recrystallized from
hexane. Physical and spectral data are shown below.
5-Acetyl-2-methoxy-4-phenylazo-N,N-diethylaniline
3. Experimental
Melting points were measured with a Yanagimoto MP-S2
micro-melting-point apparatus. NMR spectra were taken on
a Jeol a-400 spectrometers. Mass spectra were measured
with Shimadzu QP-1000 and 9020-DF spectrometers. UV
spectra were taken on Shimadzu UV-160A and Hitachi U-
4000 spectrometers. A thermal analysis was performed with
a Perkin-Elmer DSC-7 instrument. The refractive index was
determined by a Mizojiri Kogaku DVA-36VWLD ellips-
ometer. The ®lm thickness was measured with Dektak 3030
surface pro®le measuring system.
1
yield 38%; mp 105±1078C; H NMR (CDCl3) ꢇˆ1.19 (t,
Jˆ6.7 Hz, 6H), 2.25 (s, 3H), 3.40 (q, Jˆ6.7 Hz, 4H), 3.90 (s,
3H), 7.36 (s, 1H), 7.40±7.50 (m, 3H), 7.76±7.80 (m, 2H),
8.25 (s, 1H), 10.11 (s, 1H); EIMS (70 eV) m/z (rel. intensity)
‡
340 (M ; 83), 325 (100), 77 (19).
5-Acetyl-2-methoxy-4-(4-nitrophenylazo)-N,N-diethyl-
aniline yield 82%; mp 163±1658C; 1H NMR (CDCl3)

210
M. Matsui et al. / Journal of Fluorine Chemistry 97 (1999) 207±212
Table 2
(t, Jˆ7.0 Hz, 6H), 2.25 (s, 3H), 3.40 (q, Jˆ7.0 Hz, 4H), 3.89
Selected bond lengths, angles, torsion angles and dihedral angles for 3b
(s, 3H), 7.33 (s, 1H), 7.78±7.90 (m, 2H), 8.24 (s, 1H), 9.99
(s, 1H); EIMS (70 eV) m/z (rel. intensity) 358 (M ; 91), 343
(100), 95 (43).
‡
Ê
Length (A)
Bond
(a) Bond lengths
C1±C2
5-Acetyl-2-methoxy-4-[4-(tri¯uoromethyl)phenylazo]-
N,N-diethylaniline yield 18%; mp 113±1148C; 1H NMR
(CDCl3) ꢇˆ1.22 (t, Jˆ7.0 Hz, 6H), 2.26 (s, 3H), 3.45 (q,
Jˆ7.0 Hz, 4H), 3.89 (s, 3H), 7.35 (s, 1H), 7.73 (d, Jˆ8.4 Hz,
2H), 7.83 (d, Jˆ8.4 Hz, 2H), 8.23 (s, 1H), 10.06 (s, 1H);
1.326(8)
1.783(7)
1.783(8)
1.523(12)
1.168(11)
1.513(11)
1.733(6)
1.757(7)
1.552(11)
1.153(10)
1.514(11)
S1±C7
S2±C27
C30±N21
N21±N22
N22±C33
C1±S1
‡
EIMS (70 eV) m/z (rel. intensity) 408 (M ; 83), 393 (100),
145 (16).
C2±S2
C10±N11
N11±N12
N12±C13
5-Acetyl-2-methoxy-4-[4-(tri¯uoromethoxy)phenylazo]-
N,N-diethylaniline yield 85%; mp 109±1108C; 1H NMR
(CDCl3) ꢇˆ1.20 (t, Jˆ7.1 Hz, 6H), 2.26 (s, 3H), 3.42
(q, Jˆ7.1 Hz, 4H), 3.89 (s, 3H), 7.32 (s, 1H), 7.33 (d,
Jˆ8.5 Hz, 2H), 7.80 (d, Jˆ8.5 Hz, 2H), 8.24 (s, 1H),
Bond
Angle (8)
(b) Bond angles
C1±S1±C7
‡
9.99 (s, 1H); EIMS (70 eV) m/z (rel. intensity) 424 (M ;
105.1(3)
104.6(7)
104.8(7)
102.1(3)
106.9(7)
107.3(7)
C10±N11±N12
N11±N12±C±13
C2±S2±C27
77), 409 (100).
1,2-Bis[4-[2-acetyl-4-(diethylamino)-3-methoxy]phenyl-
azo]phenylthio]per¯uoro-1-cyclopentene yield 32%; mp
103±1078C; 1H NMR (CDCl3) ꢇˆ1.21 (t, Jˆ7.0 Hz,
12H), 2.26 (s, 6H), 3.44 (q, Jˆ7.0 Hz, 8H), 3.88 (s, 6H),
7.32 (s, 2H), 7.59 (d, Jˆ8.5 Hz, 4H), 7.75 (d, Jˆ8.5 Hz,
4H), 8.22 (s, 2H), 10.08 (s, 2H); EIMS (70 eV) m/z (rel.
C30±N21±N22
N21±N22±C33
Bond
Angle (8)
Configuration
(c) Torsion angles
S1±C1±C2±S2
C2±C1±S1±C7
‡
0.1(6)
178.0(6)
51.9(7)
cis
intensity) 916 (M ; 1), 443 (16), 250 (100).
trans
gauche
trans
trans
C1±C2±S2±C27
3.2. Synthesis of 1,2-bis(4-aminophenylthio)-
perfluorocycloalkenes 2
C10±N11±N12±C13 (Azo1)
C30±N21±N22±C33 (Azo2)
177.0(8)
177.3(9)
Planea
Angle (8)
To a DMF (10 ml) solution of 4-aminothiophenol (1.25 g,
10 mmol) was added 60% sodium hydride (0.4 g, 10 mmol).
The mixture was stirred for 30 min at 788C under a
nitrogen atmosphere. To the mixture was added 1,2-dichloro-
per¯uorocycloalkene (5 mmol) and the mixture was stirred
overnight under a nitrogen atmosphere. After the reaction
was completed, the mixture was poured into water (100 ml)
and extracted with dichloromethane (100 mlÂ2). The
extract was washed with water (100 mlÂ6) and
dried. After evaporation of the solvent, the product was
isolated by column chromatography (SiO2, CH2Cl2) and
recrystallized from hexane. Physical and spectral data are
shown below.
(d) Dihedral angles
CP±Ph1
85.9
7.2
Ph1±Azo1
Azol±Ph2
Ph1±Ph2
8.2
15.4
69.1
16.8
19.7
36.4
Cp±Ph3
Ph3±Azo2
Azo2±Ph4
Ph3±Ph4
a Constitution atoms of the planes. CP: C1, C2, C3, C4, C5; Ph1: C7, C8,
C9, C10, C11, C12; Ph2: C13, C14, C15, C16, C17, C18; Ph3: C27, C28,
C29, C30, C31, C32; Ph4: C33, C34, C35, C36, C37, C38; Azo1: C10,
N11, N12, C13; Azo2: C30, N21, N22, C33.
1,2-Bis(4-aminophenylthio)per¯uorocyclobutene (2a).
Yield 23%; mp 71±728C; 1H NMR (CDCl3) ꢇˆ3.77 (s,
4H), 6.59 (d, Jˆ8.5 Hz, 4H), 7.26 (d, Jˆ8.5 Hz, 4H); EIMS
ꢇˆ1.25 (t, Jˆ7.0 Hz, 6H), 2.28 (s, 3H), 3.50 (q, Jˆ7.0 Hz,
4H), 3.89 (s, 3H), 7.33 (s, 1H), 7.83 (d, Jˆ9.1 Hz, 2H), 8.21
(s, 1H), 8.34 (d, Jˆ9.1 Hz, 2H), 10.13 (s, 1H); EIMS
‡
(70 eV) m/z (rel. intensity) 372 (M ; 6), 248 (100), 124 (94).
‡
(70 eV) m/z (rel. intensity) 385 (M ; 58), 370 (100).
1,2-Bis(4-aminophenylthio)per¯uorocyclopentene (2b).
1
5-Acetyl-4-(4-chlorophenylazo)-2-methoxy-N,N-diethyl-
aniline yield 71%; mp 117±1198C; 1H NMR (CDCl3)
ꢇˆ1.19 (t, Jˆ7.1 Hz, 6H), 2.26 (s, 3H), 3.41 (q, Jˆ7.1 Hz,
4H), 3.89 (s, 3H), 7.33 (s, 1H), 7.46 (d, Jˆ8.5 Hz, 2H), 7.72
(d, Jˆ8.5 Hz, 2H), 8.23 (s, 1H), 10.13 (s, 1H); EIMS
Yield 20%; mp 117±1188C; H NMR (CDCl3) ꢇˆ3.87 (s,
4H), 6.63 (d, Jˆ8.7 Hz, 4H), 7.35 (d, Jˆ8.7 Hz, 4H); EIMS
‡
(70 eV) m/z (rel. intensity) 422 (M ; 73), 149 (32), 124
(100).
1,2-Bis(4-aminophenylthio)per¯uorocyclohexene (2c).
1
‡
‡
(70 eV) m/z (rel. intensity) 376 (M ‡2; 26), 374 (M ;
Yield 17%; mp 122±1238C; H NMR (CDCl3) ꢇˆ3.86 (s,
79), 361 (35), 359 (100).
5-Acetyl-4-(4-¯uorophenylazo)-2-methoxy-N,N-diethyl-
aniline yield 29%; mp 76±788C; 1H NMR (CDCl3) ꢇˆ1.19
4H), 6.62 (d, Jˆ8.3 Hz, 4H), 7.32 (d, Jˆ8.3 Hz, 4H); EIMS
‡
(70 eV) m/z (rel. intensity) 472 (M ; 100), 184 (27), 124
(38).

M. Matsui et al. / Journal of Fluorine Chemistry 97 (1999) 207±212
211
Table 3
Absorption band and d33 values of NLOphores doped in polymers
R1
R2
ꢁa
In PMMAb
In PCc
a
ꢃmax (nm)
NLOphore
n
ꢃmax (nm)
d33 (pm)
ꢃmax (nm)
d33 (pm)
3a
3b
3c
5b
2
3
4
3
N(C2H5)C2H4OH
N(C2H5)C2H4OH
N(C2H5)C2H4OH
NO2
N(C2H5)C2H4OH
N(C2H5)C2H4OH
N(C2H5)C2H4OH
N(C2H5)C2H4OH
438
441
440
442
351
482
46 000
53 000
77 000
32 000
28 700
27 000
444
443
447
457
11
32
19
6
431
430
442
d
27
48
20
d
DR1
±
±
±
491
16
487
19
a Measured in ethanol.
b 1.5 Mol% of NLOphore.
c 3.0 Mol% of NLOphore.
d Not measured.
3.3. Synthesis of 1,2-bis[4-[4-[N-ethyl-N-(2-
hydroxyethyl)amino]phenylazo]phenyl-
thio]perfluorocycloalkenes 3a±c
Jˆ5.7 Hz, 4H), 3.88 (q, Jˆ5.7 Hz, 4H), 6.80 (d, Jˆ9.2 Hz,
4H), 7.56 (d, Jˆ8.6 Hz, 4H), 7.81 (d, Jˆ8.6 Hz, 4H), 7.86
(d, Jˆ9.2 Hz, 4H); EIMS (70 eV) m/z (rel. intensity) 774
‡
(M ; 13), 743 (27), 715 (17), 599 (18), 568 (59), 358 (100)
To an acetone±water mixed solution (1:1, 20 ml) of
conc. hydrochloric acid (1.13 ml, 13.6 mmol) was added
1,2-bis(4-aminophenylthio)per¯uorocycloalkenes 2
(1.5 mmol). The mixture was stirred for 1 h at room tem-
perature and then cooled to 08C. To the mixture was added
an aqueous solution (10 ml) of sodium nitrite (0.25 g,
3.6 mmol) and the mixture was stirred for 30 min at 08C.
After the reaction was completed, to the mixture was added
an acetone solution (15 ml) of N-ethylanilinoethanol
(0.56 g, 3.4 mmol) and the mixture was stirred for 1 h.
The pH value of the mixture was adjusted at 7.0 with an
aqueous sodium hydroxide solution. The resulting precipi-
tate was ®ltered, puri®ed by column chromatography (SiO2,
CH3COOC2H5), and recrystallized from dichloromethane.
Physical and spectral data are shown below.
134 (28). Found: C, 57.42; H, 4.61; N, 10.82. Calcd. for
C37H36F6N6O2S2: C, 57.35; H, 4.68; N, 10.85.
1,2-Bis[4-[4-[N-ethyl-N-(2-hydroxyethyl)amino]phenyl-
azo]phenylthio]per¯uorocyclohexene (3c). Yield 28%; mp
1
138±1438C; H NMR (CDCl3) ꢇˆ1.24 (t, Jˆ7.1 Hz, 6H),
1.67 (t, Jˆ5.6 Hz, 2H), 3.54 (q, Jˆ7.1 Hz, 4H), 3.59 (t,
Jˆ5.6 Hz, 4H), 3.88 (q, Jˆ5.6 Hz, 4H), 6.78 (d, Jˆ9.2 Hz,
4H), 7.51 (d, Jˆ8.5 Hz, 4H), 7.80 (d, Jˆ8.5 Hz, 4H), 7.85
(d, Jˆ9.2 Hz, 4H); EIMS (70 eV) m/z (rel. intensity) 824
‡
(M ; 10), 793 (23), 764 (20), 617 (30), 381 (95),133 (100).
Found: C, 55.67; H, 4.52; N, 10.22. Calcd. for
C38H36F8N6O2S2: C, 55.33; H, 4.40; N, 10.19.
3.4. Synthesis of 1-(4-aminophenylthio)-2-[4-
(nitrophenylazo)phenylthio]perfluorocyclopentene
(4b)
1,2-Bis[4-[4-[N-ethyl-N-(2-hydroxyethyl)amino]phenyl-
azo]phenylthio]per¯uorocyclobutene (3a). Yield 25%; mp
1
174±1778C; H NMR (CDCl3) ꢇˆ1.24 (s, Jˆ7.1 Hz, 6H),
To an acetic acid solution (10 ml) of 1,2-bis(4-amino-
phenylthio)per¯uorocyclopentene 2b (1.06 g, 2.5 mmol)
was added 4-nitrosonitrobenzene (0.38 g, 2.5 mmol) and
the mixture was stirred overnight at room temperature. After
the reaction was completed, the mixture was poured into
water. The resulting precipitate was ®ltered, dried, puri®ed
by column chromatography (SiO2, CH2Cl2), and recrystal-
lized from a chloroform±hexane mixed solution. Yield 38%;
mp 134±1358C; 1H NMR (CDCl3) ꢇˆ3.93 (s, 2H), 6.63 (d,
Jˆ8.3 Hz, 2H), 7.31 (d, Jˆ8.5 Hz, 2H), 7.58 (d, Jˆ8.5 Hz,
2H), 7.96 (d, Jˆ8.3 Hz, 2H), 8.05 (d, Jˆ8.5 Hz, 2H), 8.40
(d, Jˆ8.5 Hz, 2H); EIMS (70 eV) m/z (rel. intensity) 556
1.60 (t, Jˆ5.6 Hz, 2H), 3.55 (q, Jˆ7.1 Hz, 4H), 3.60 (t,
Jˆ5.6 Hz, 4H), 3.87 (q, Jˆ5.6 Hz, 4H), 6.80 (d, Jˆ9.2 Hz,
4H), 7.56 (d, Jˆ8.4 Hz, 4H), 7.80 (d, Jˆ8.4 Hz, 4H), 7.86
(d, Jˆ9.2 Hz, 4H); EIMS (70 eV) m/z (rel. intensity) 724
‡
(M ; 38), 693 (44), 664 (17), 649 (31), 548 (32), 517 (100),
331 (88), 301 (18), 270 (58), 149 (23), 133 (73). Found: C,
59.58; H, 4.86; N, 11.75. Calcd. for C36H36F4N6O2S2: C,
59.65; H, 5.01; N, 11.59.
1,2-Bis[4-[4-[N-ethyl-N-(2-hydroxyethyl)amino]phenyl-
azo]phenylthio]per¯uorocyclopentene (3b). Yield 22%; mp
1
147±1498C; H NMR (CDCl3) ꢇˆ1.24 (t, Jˆ7.1 Hz, 6H),
‡
1.64 (t, Jˆ5.7 Hz, 2H), 3.56 (q, Jˆ7.1 Hz, 4H), 3.60 (t,
(M ; 99), 373 (26), 298 (35), 199 (100).

212
M. Matsui et al. / Journal of Fluorine Chemistry 97 (1999) 207±212
3.5. Synthesis of 1-[4-[4-[N-ethyl-N-(2-
hydroxyethyl)amino]phenylazo]phenylthio]-2-[4-(4-
nitrophenylazo)phenylthio]perfluorocyclopentene
(5b)
3.8. X-ray crystallographic analysis
Single crystals of suitable quality for X-ray diffraction
were obtained from a mixed solution of chloroform and
hexane at room temperature. Intensity data were collected
on a MAC SCIENCE diffractometer by use of Mo Kꢄ
To an acetone±water mixed solution (1:1, 20 ml) of conc.
hydrochloric acid (0.34 ml, 4.1 mmol) was added 1-(4-
aminophenylthio)-2-[4-(nitrophenylazo)phenylthio]per-
¯uorocyclopentene 4b (0.50 g, 0.9 mmol). The mixture was
stirred for 1 h at room temperature and then cooled to 08C.
To the solution was added an aqueous solution (10 ml) of
sodium nitrite (0.077 g, 1.1 mmol) and the mixture was
stirred for 30 min at 08C. After the reaction, to the mixture
was added an acetone solution (15 ml) of N-ethylanilino-
ethanol (0.165 g, 1.0 mmol) and the mixture was stirred
for 1 h. The pH value of the mixture was adjusted at 7.0 with
an aqueous sodium hydroxide solution. The resulting pre-
cipitate was ®ltered, puri®ed by column chromatography
(SiO2, CH3COOC2H5), and recrystallized from a chloro-
form±hexane mixed solution. Yield 47%; mp 136±1388C;
1H NMR (CDCl3) ꢇˆ1.25 (t, Jˆ7.1 Hz, 3H), 1.60 (t,
Jˆ5.8 Hz, 1H), 3.55 (q, Jˆ7.1 Hz, 2H), 3.61 (t, Jˆ5.8 Hz,
2H), 3.89 (q, Jˆ5.8 Hz, 2H), 6.80 (d, Jˆ9.1 Hz, 2H), 7.56
(d, Jˆ8.5 Hz, 2H), 7.59 (d, Jˆ8.5 Hz, 2H), 7.81 (d,
Jˆ8.5 Hz, 2H), 7.86 (d, Jˆ9.1 Hz, 2H), 7.96 (d, Jˆ8.5 Hz,
2H), 8.05 (d, Jˆ9.1 Hz, 2H), 8.40 (d, Jˆ9.1 Hz, 2H); EIMS
Ê
radiation (ꢃˆ0.71073 A) in the range of 2ꢈ less than 538.
Altogether 6785 independent re¯ections were measured.
3498 Re¯ections of these intensities were exceeded their
standard deviations three times and considered as observed
to use in the structure determination. Throughout the
structure determination the program package CRYSTAN
GM (MAC SCIENCE) was used. Anisotropic thermal
vibrations were assumed for the non-hydrogen atoms. All
the hydrogen atoms, except the hydroxy hydrogen atoms,
were found from a difference Fourier map and re®ned
isotropically. The ®nal residual index R and weighted index
Rw were 0.072 and 0.064, respectively. The goodness-of-®t
was 1.246.
Table of the atomic coordinates and the temperature
factors will be obtained from the author with asterisk on
request.
References
‡
[1] J.L. Oudar, J. Chem. Phys. 67 (1977) 446.
(70 eV) m/z (rel. intensity) 732 (M ; 13), 701 (60), 133
[2] T.-A. Chen, A.K.-Y. Jen, Y. Cai, Macromolecules 29 (1996) 535.
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Mater. 4 (1992) 1253.
(100). Found: C, 54.13; H, 3.42; N, 11.44. Calcd. for
C33H26F6N6O2S3: C, 54.09; H, 3.58; N, 11.67.
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[5] K. Hirota, M. Hosoda, B. Joglekar, M. Matsui, H. Muramatsu, Jpn. J.
Appl. Phys. 32 (1993) L1811.
3.6. Film preparation
[6] B. Joglekar, K. Shibata, H. Muramatsu, M. Matsui, K. Hirota, M.
Hosoda, K. Tai, Polym. J. 29 (1997) 184.
The NLOphores (1.5 mol% in PMMA, 3.0 mol% in PC)
were dissolved in a dichloromethane solution of the polymer
matrix. The mixture was put on an ITO glass and spin-
coated (600 rpm, 20 s). After drying the ®lm under reduced
pressure overnight, the ®lms were poled (6 kV cm 1, 2 min)
at 110 (PMMA) and 1508C (PC). The thickness of the ®lms
were about 2000 (PMMA) and 1500 (PC) A, respectively.
After cooling the ®lm, the applied high voltage was
removed.
[7] K. Hirota, M. Hosoda, K. Tai, B. Joglekar, M. Matsui, H.
Muramatsu, Mol. Cryst. Liq. Cryst. 267 (1995) 83.
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Volksen, Science 268 (1995) 1604.
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[10] F. Pan, M.S. Wong, V. Gramlich, C. Bosshard, P. GuÈnter, J. Am.
Chem. Soc. 118 (1996) 6315.
Ê
[11] S.R. Morder, L.-T. Cheng, B.G. Tiemann, A.C. Friedli, M.B. Desce,
J.W. Perry, J. Skindhùj, Science 263 (1994) 511.
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Sugihara, C. Egami, Appl. Phys. Lett. 69 (1996) 2813.
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Chem. Commun. (1995) 969.
3.7. Second harmonic generation (SHG) measurement
The SHG of the ®lm was measured by the Maker fringe
method using a Q-switched Nd:YAG laser (ꢃˆ1064 nm). A
1 mm thick y-cut quartz (d11ˆ0.33 pm V 1) was used as the
reference. The second-order NLO coef®cient (d33) was
determined by the mean square methods using the relation-
ship of the second harmonic light intensity and the incident
angle of the poled ®lm as described in our previous papers
[14±16].
[14] M. Matsui, Y. Marui, M. Kushida, K. Funabiki, K. Shibata, H.
Muramatsu, K. Hirota, M. Hosoda, K. Tai, Dyes Pigm. 38 (1998)
57.
[15] M. Matsui, M. Kushida, K. Funabiki, K. Shibata, H. Muramatsu, K.
Hirota, M. Hosoda, K. Tai, Dyes Pigm. 37 (1998) 283.
[16] M. Matsui, R. Kawase, K. Funabiki, H. Muramatsu, K. Shibata, Y.
Ishigure, K. Hirota, M. Hosoda, K. Tai, Bull. Chem. Soc., Jpn. 70
(1997) 3153.