Solid-state fluorescence of pyridinium styryl dyes

Article abstract of DOI:10.1016/j.dyepig.2013.07.026

1-Alkyl-2-[4-(diethylamino)styryl]pyridinium salts showed fluorescence maxima at around 650 nm in the solid state depending on the alkyl group and counter anion. 1-Butyl-2-[4-(diethylamino)styryl]pyridinium bis(perfluorobutylsulfonyl)imide exhibited the fluorescence maximum at 652 nm with the highest quantum yield 0.16 in the crystalline form. The single X-ray crystallography suggests that this compound exhibits isolated dimer-type packing leading to fluorescence in the solid state.

Full text of DOI:10.1016/j.dyepig.2013.07.026

Dyes and Pigments 99 (2013) 916e923
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Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Solid-state fluorescence of pyridinium styryl dyes
,
a
a
a
Masaki Matsui a , Kohtaro Ooiwa , Ayumi Okada , Yasuhiro Kubota ,
*
Kazumasa Funabiki a, Hiroyasu Sato b
a Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
b X-ray Research Laborator, Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima, Tokyo 196-8666, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
1-Alkyl-2-[4-(diethylamino)styryl]pyridinium salts showed fluorescence maxima at around 650 nm in
the solid state depending on the alkyl group and counter anion. 1-Butyl-2-[4-(diethylamino)styryl]pyr-
idinium bis(perfluorobutylsulfonyl)imide exhibited the fluorescence maximum at 652 nm with the
highest quantum yield 0.16 in the crystalline form. The single X-ray crystallography suggests that this
compound exhibits isolated dimer-type packing leading to fluorescence in the solid state.
Ó 2013 Elsevier Ltd. All rights reserved.
Received 3 June 2013
Received in revised form
18 July 2013
Accepted 19 July 2013
Available online 2 August 2013
Keywords:
Solid-state fluorescence
Styryl dyes
Counter anion
p/p-interactions
Single X-ray crystallography
Cationic dyes
1. Introduction
2. Results and discussion
Cationic styryl dyes are interesting compounds having po-
tential applications for fluorescence probes [1e5], sensitizers
[6,7], sensors [8], two-photon absorption materials [9], non-
linear optical materials [10,11], information recording materials
[12], and radical initiators [13]. The effect of an alkyl group in
pyridinium styryl dyes on the solvatochromism [14] and the af-
finity for surfactants have been reported [15,16]. Though many
papers concerning solid-state fluorescence have been reported,
there is one paper describing the solid-state fluorescence of
cationic compounds [17]. In the case of neutral fluorescent
compounds, there are few compounds showing Fmax beyond
700 nm. Cationic styryl dyes are easily prepared and can exhibit a
wide range Fmax by changing the electron-withdrawing ability of
cationic heteroaromatic ring and electron-donating force of
another aromatic moiety. Thus cationic styryl dyes have potential
applications as solid-state fluorescent materials. We report
herein the solid-state fluorescence of 1-alkyl-2-[4-(dieth-
ylamino)styryl]pyridinium dyes.
2.1. Synthesis
Scheme 1 shows the synthesis of pyridinium styryl dyes 15e20
and 25e33. 2-Methylpyridine (1) was N-alkylated with alkyl ha-
lides 2e7 to give 1-alkyl-2-methylpyridinium halides 8e13, which
were condensed with 4-(diethylamino)benzaldehyde (14) in the
presence of piperidine to afford 15e20. Then, these compounds
were treated with lithium salts 21e24 to provide dyes 25e33.
2.2. UVevis absorption and fluorescence spectra
The UVevis absorption and fluorescence spectra of 17 and 25e
33 in dichloromethane are shown in Fig. 1. The absorption
maximum (lmax) was observed at around 510 nm with a molar
absorption coefficient (ε) in the range of 39,400 to
45,500 molꢀ1 dm3 cmꢀ1. The fluorescence maximum (Fmax) was
observed at around 594 nm with fluorescence quantum yields (Ff
)
in the range 0.10e0.12. Thus, no significant differences in the UVe
vis absorption and fluorescence spectra were observed in solution.
The fluorescence spectra of 17 and 25e33 in the crystalline form
are depicted in Fig. 2. Compounds 17 and 29 were recrystallized
from toluene. Compounds 26 and 32 were from hexaneeethyl ac-
etate mixed solvent. The other compounds were recrystallized from
* Corresponding author.
E-mail address: matsuim@gifu-u.ac.jp (M. Matsui).
0143-7208/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dyepig.2013.07.026

M. Matsui et al. / Dyes and Pigments 99 (2013) 916e923
917
OHC
ii)
iii)
LiY
NEt2
i)
RX
14
21-24
2-7
N
R
N
N
R
Me
N
Me
R
NEt2
Y
NEt2
X
X
1
8-13
15-20
25-33
X
Y
Compd
Compd
R
Y
Compd
Compd
R
R
X
I
21
22
23
24
CF3SO3
2,
3,
8
9
Me
Et
Bu
Oct
Dodec
Octadec
(C4F9SO2)2N
(C4F9SO2)2N
CF3SO3
(CF3SO2)2N
(CF2)3(SO2)2N
(C4F9SO2)2N
(C4F9SO2)2N
(C4F9SO2)2N
(C4F9SO2)2N
15
16
17
18
19
20
25
26
27
28
29
30
31
32
33
Me
Et
Bu
Oct
Dodec
Octadec
Me
Et
Bu
Bu
Bu
Bu
Oct
Dodec
I
Br
Br
I
I
I
(CF2)3(SO2)2N
(CF3SO2)2N
(C4F9SO2)2N
Br
Br
I
I
I
4, 10
5, 11
6, 12
7, 13
Octadec
Scheme 1. Reagents and conditions: (i) 1 (1.0 eq), 2e7 (1.1 eq), alcohols, reflux, 5 d, (ii) 8e13 (1.0 eq), 14 (1.0 eq), piperidine, EtOH, reflux, 3 d, (iii) 15e20 (1.0 eq), 21e24 (1.25 eq),
water/acetone ¼ 2/1, r.t., 1 d.
hexane. The Fmax was observed in the range of 641e677 nm, there
being bathochromic compared to those in dichloromethane (593e
595 nm), indicating the intermolecular interactions in the solid
state.
on the pyridinium-nitrogen, the X-ray crystallography of 17, 25, and
30 was performed.
The X-ray crystallography of 17 is shown in Fig. 3. Molecules are
arranged in parallel. Molecules A and B form a head-to-tail dimer
The solid-state fluorescence of 1-butyl-2-[4-(diethylamino)
styryl]pyridinium dyes 17, 27, 28, 29, and 30 are indicated in Fig. 2a.
The fluorescence was more intense in the order of the counter
with
p
ꢀ
/
p
interactions (top view (1)). The interplanar distance is
3.43 A (side view). Molecule C is also packed in parallel for B. The
interactions are observed at the edge of p-(diethylamino)phe-
p
/
p
ꢀ
anion: (C4F9SO2)2N (30, Ff
¼
0.16)
>
(CF2)3(SO2)2N (29,
nylene rings of B and C with interplanar distance 3.95 A (top view
(2) and side view). The cationic fluorophore has two short contacts
with neighboring bromo anions. The distance between the a-car-
bon on the N-butyl group in the pyridinium moiety of B and bromo
anion E is 3.68 A (overview (1) and (2)). The distance between the
olefinic bond and another bromo anion D is 3.85 A. As a bromo
anion is smaller than the other anions in this study, the
teractions is a main factor for the packing. Thus, compound 17 has
consequent interactions (side view).
0.10) > CF3SO3 (27, 0.07), (CF3SO2)2N (28, 0.04), and Br (17, 0.02).
The solid-state fluorescence of 1-alkyl-2-[4-(diethylamino)styryl]
pyridinium bis(perfluorobutylsulfonyl)imides 25, 26, 27, 30, 32, and
33 are also shown in Fig. 2b. The fluorescence of Et (26, 0.14) and Bu
(30, 0.16) derivatives were more intense than those of Me (25, 0.03),
Octyl (31, 0.05), Dodecyl (32, 0.03), and Octadecyl (33, 0.08) de-
rivatives (Table 1).
ꢀ
ꢀ
p/p in-
p/p
2.3. X-ray crystallography
The X-ray crystal structure of 25 is shown in Fig. 4. Molecules
form a pair of head-to-tail dimers and are packed in parallel. Bis(-
perfluorobutylsulfonyl)imido anions are located beside the cationic
fluorophores. The cationic fluorophore has three short contacts
To understand why the solid-state fluorescence intensity of
styryl dyes depends on the counter anion and the alkyl substituent
(a)
(b)
N
R
N
Bu
NEt2
NEt2
Y (X)
(C4F9SO2)2N
1
1
17 1500
25
26
30
31
32
33
1500
1000
500
0
0.8
0.6
0.4
0.2
0
27
28
29
30
0.8
0.6
0.4
0.2
0
1000
500
0
500
600
700
500
600
700
Wavelength / nm
Wavelength / nm
Fig. 1. UVevis absorption and fluorescence spectra (a) change in Y (ꢁ) and (b) change in R. Measured on 1.0 ꢁ 10ꢀ5 mol dmꢀ3 at 25 ꢂC in dichloromethane. Solid and dotted lines
represent fluorescence and UVevis absorption spectra, respectively.

918
M. Matsui et al. / Dyes and Pigments 99 (2013) 916e923
(a)
(b)
N
R
N
Bu
NEt2
NEt2
(C4F9SO2)2N
Y (X)
1000
800
600
400
200
0
1000
25
17
30
26
30
26
30
31
32
33
800
600
400
200
0
27
28
29
30
29
27
33
31
25
32
25
28
17
17
700
Wavelength / nm
500
600
800
500
600
700
800
Wavelength / nm
Fig. 2. Solid-state fluorescence spectra (a) change in Y (ꢁ) and (b) change in R. Solid and dotted lines represent fluorescence and excitation spectra, respectively.
with adjacent anions. The carbon atom at the 3-position on the
intense fluorescence than 25 and 30. These results suggest that the
cation-anion Coulomb interactions are not the main factor affecting
the fluorescence intensity in the solid state.
pyridinium ring and the olefinic bond of B has interactions with one
ꢀ
of the sulfonyl-oxygen of the anion E with length 3.42 and 3.38 A,
respectively (overview (1)). The carbon atom at the 2-position on
In the case of neutral compounds, consequent p/p interactions
the p-(diethylamino)phenylene ring of B also has interactions with
one of the oxygen atom of another sulfonyl group in D with 3.53 A
and intermolecular hydrogen bonding of the fluorophore reduce
the solid-state fluorescence intensity. Therefore, it is quite
reasonable to consider that as cationic fluorophores of 17 and 25
ꢀ
(overview (1) and (2)). Molecules A and B have
p
/
p
interactions
with interplanar distance 3.52 A (top view (1) and side view).
Molecules B and C also have interactions with interplanar
ꢀ
have consecutive
p/p stacking to show weak intensity compared
p
/p
with 30, which has isolated dimer-type packing.
ꢀ
distance 3.47 A (top view (2) and side view). The N-methyl group is
located on the same plane to the styryl skeleton not to sterically
hinder the adjacent cationic fluorophores (side view). As the result,
Meanwhile, the solid-state fluorescence intensity also depends
on the melting point [18]. In low-melting point compounds, the
stretching, vibration, and rotation of chemical bonds can occur to
accelerate the non-radiation process from S1 state to S0 state. The
melting points of 17, 25, and 30 are 249, 132, and 81.6 ꢂC, respec-
tively. It is suspected that, in the case of 31, 32, and 33, as the
melting point is low (55.2e70.2 ꢂC), the fluorescence intensity is
low. Therefore, the balance between the intermolecular in-
teractions and its melting point is important for intensely solid-
state fluorescent compounds. Compounds 17, 25, and 30 form the
dimers in the crystalline form. No emission peak was observed for
these compounds beyond 800 nm, indicating no fluorescence from
the eximer. Therefore, the molecular design of styryl dyes forming
isolated monomer-type packing with medium melting point is
required to obtain more intense solid-state fluorescent styryl dyes.
consequent
The single X-ray crystal structure of 30 is shown in Fig. 5. Mole-
cules form a pair of head-to-tail dimers with interactions and are
p/p interaction is observed for 25 (side view).
p/p
ꢀ
packed in parallel. The interplanar distance between A and B is 3.38 A
(top view (1) and side view). Though molecules C is packed in parallel
ꢀ
for B, the interplanar distance is 4.81 A being too long to have
p/p
interactions (top view (2) and side view). Bis(perfluorobutylsulfonyl)
imido anions are located beside the cationic fluorophores. Cationic
fluorophore has four short contacts with adjacent anions. The a-
carbon at the pyridinium ring, olefinic bond, and carbon atom at the
2-position in p-(diethylamino)phenylene ring of B have interactions
with one of the sulfonyl-oxygen of E with distances of 3.51, 3.47, and
ꢀ
3.37 A, respectively (overview (1) and (2)). The carbon atom at the 3-
position in the pyridinium ring of B has interactions with imido-
nitrogen of another adjacent anion D. The packing direction of the
anions in 30 is different from that in 25. In the case of 30, the N-butyl
group could sterically hinder the neighboring dimer units preventing
3. Conclusion
1-Butyl-2-[4-(diethylamino)styryl]pyridinium bis(perfluorobut
ylsulfonyl)imide exhibited a fluorescence maximum at 652 nm
with the highest fluorescence quantum yield of 0.16 among any
derivatives in the solid state. The X-ray crystal structure suggests
that this compound has isolated dimer-type packing leading to
intense solid-state fluorescence.
p/p
interactions among the units. Then, one side of per-
fluorobutylsulfonyl moiety can hinder the pyridinium styryl fluo-
rophores packing in parallel. As a result, no consequent
p/p
interactions are observed for 30. Compound 30 has isolated dimer-
type packing (side view).
The fluorophores of styryl dyes have interactions with both the
counter anions and the neighboring cationic fluorophores. A bromo
anion is smaller than the other imido anions. The cationic fluo-
rophores of 17, 25, and 30 have two, three, and four short contacts
with anions as shown in Figs. 3e5, respectively. The cation-anion
4. Experimental
4.1. Instruments
Melting points were measured with Yanagimoto MP-52 micro-
melting point apparatus and SII Technology Co., EXSTAR-6200 in-
strument. NMR spectra were obtained by a JEOL JMN
ꢀ
contacts (3.68 and 3.85 A) in 17 is significantly long compared
ꢀ
with those of 25 (3.38, 3.42, and 3.53 A) and 30 (3.37, 3.47, 3.51, and
a-400 spec-
ꢀ
3.62 A). The Coulomb interactions are inversely proportional to the
trometer. IR spectra were taken on Shimadzu Affinity-1
a
square of the bond length. Thus, compounds 25 and 30 have
stronger cation-anion interactions than 17. However, 17 shows less
spectrophotometer. Elemental analysis was performed on Yanaco
CHN corder MT-6. UVevis absorption and fluorescence spectra

M. Matsui et al. / Dyes and Pigments 99 (2013) 916e923
919
Table 1
Physical properties of pyridinium styryl dyes.
Compd
R
Y (X)
mp/ꢂC
In dichloromethanea
Solid state
εx/nm
lmax/nm (ε)
Fmax/nm
Ffb
l
Fmax/nm
Ffb
17
25
26
27
28
29
30
31
32
33
Bu
Me
Et
Bu
Bu
Bu
Bu
Oct
Dodec
Octadec
Br
249e250
132e133
118e119
152e153
121e122
140e141
81.6
70.2
55.2
65.4
508 (41,600)
514 (42,200)
510 (41,600)
510 (44,200)
512 (40,600)
512 (40,500)
508 (41,800)
512 (39,400)
511 (45,500)
512 (41,800)
595
595
595
593
594
594
595
593
595
593
0.10
0.11
0.11
0.12
0.12
0.12
0.11
0.11
0.11
0.11
557
588
554
565
574
560
529
555
580
548
677
677
662
652
665
654
652
651
643
664
0.02
0.03
0.14
0.07
0.04
0.10
0.16
0.05
0.03
0.08
(C4F9SO2)2N
(C4F9SO2)2N
CF3SO3
(CF3SO2)2N
(CF2)3(SO2)2N
(C4F9SO2)2N
(C4F9SO2)2N
(C4F9SO2)2N
(C4F9SO2)2N
a
Measured on 1 ꢁ 10ꢀ5 mol dmꢀ3 of substrate at 25 ꢂC.
b
Determined by a Hamamatsu Photonics Quantaurus-QY.
Fig. 3. Single X-ray crystallography of 17.

920
M. Matsui et al. / Dyes and Pigments 99 (2013) 916e923
Fig. 4. Single X-ray crystallography of 25.
were taken on Hitachi U-3500 and JASCO FP8600 spectrophotom-
eters, respectively. Fluorescence quantum yields were measured by
a Hamamatsu Photonics Quantaurus-QY.
mixture was concentrated. To the residue was added acetonitrile
and poured into ether. The resulting solid was filtered and dried to
give a white solid.
4.2. Materials
4.3.1. 1,2-Dimethylpyridinium iodide (8)
Yield 72%; mp 235e236 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 2.96
2-Methylpyridine (1) was purchased from Nacalai tesque, Inc.
Methyliodide(2),ethylbromide(3),1-bromobutane(4),1-iodooctane
(5), 1-iodododecane (6), 4-(diethylamino)benzaldehyde (14), lithium
4,4,5,5,6,6-hexafluorodihydro-4H-1,3,2-dithiazine 1,1,3,3-tetraoxide
(22), and lithium bis(perfluorobutylsulfonyl)imide (24) were pur-
chased from Wako Chemical Industries, Ltd. Octadecyl iodide (7),
lithium trifluoromethanesulfonate (21), and lithium bis(tri-
fluoromethylsulfonyl)imide (23) were purchased from TOKYO KASEI
KOGYO CO., LTD., SigmaeAldrich Co., Ltd., and Kanto Chemical Co.,
Inc., respectively.
(s, 3H), 4.54 (s, 3H), 7.91 (d, J ¼ 7.1 Hz, 1H), 7.93 (t, J ¼ 7.1 Hz, 1H),
8.37 (t, J ¼ 7.1 Hz, 1H), 9.41 (d, J ¼ 7.1 Hz, 1H).
4.3.2. 1-Ethyl-2-methylpyridinium bromide (9)
Yield 51%; mp 57.5e58.5 ꢂC; 1H NMR (400 MHz, CDCl3)
J¼ 7.3 Hz, 3H), 3.06 (s, 3H), 4.97 (t, J¼ 7.3 Hz, 2H), 8.03 (t, J¼ 7.5 Hz,1H),
8.14 (d, J ¼ 7.5 Hz, 1H), 8.52 (t, J ¼ 7.5 Hz, 1H), 9.63 (d, J ¼ 7.5 Hz, 1H).
d
¼ 1.67 (t,
4.3.3. 1-Butyl-2-methylpyridinium bromide (10)
Yield 97%; mp 149e150 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 1.00
(t, J ¼ 7.5 Hz, 3H),1.53 (sex, J ¼ 7.5 Hz, 2H),1.92 (quin, J ¼ 7.5 Hz, 2H),
2.97 (s, 3H), 4.98 (t, J ¼ 7.5 Hz, 2H), 7.90 (d, J ¼ 7.1 Hz, 1H), 8.00 (t,
J ¼ 7.1 Hz, 1H), 8.36 (t, J ¼ 7.1 Hz, 1H), 9.88 (d, J ¼ 7.1 Hz, 1H).
4.3. Synthesis of 1-alkyl-2-methylpyridinium halides 8e13
To 2-methylpyridine (1) (1.85 g, 20 mmol) (8: methanol (13 mL),
9: ethanol (13 mL), 10: 1-butanol (13 mL), 11, 12, 13: neat) was
added an alkyl halide 2e7 (22 mmol). The mixture was refluxed (5
days) or heated (overnight). In the case of 8, 9, and 10, the reaction
4.3.4. 2-Methyl-1-octylpyridinium iodide (11)
Yield 90%; mp 111e112 ꢂC; 1H NMR (400 MHz, CDCl3)
J ¼ 6.9 Hz, 3H), 1.20e1.55 (m, 10H), 1.96 (quin, J ¼ 6.9 Hz, 2H), 2.98
d
¼ 0.87 (t,

M. Matsui et al. / Dyes and Pigments 99 (2013) 916e923
921
Fig. 5. Single X-ray crystallography of 30.
(s, 3H), 4.81 (t, J ¼ 6.9 Hz, 2H), 8.02 (t, J ¼ 7.1 Hz, 1H), 8.14 (d,
4.4. Synthesis of 1-alkyl-2-[4-(diethylamino)styryl]pyridinium
halides 15e20
J ¼ 7.1 Hz, 1H), 8.53 (t, J ¼ 7.1 Hz, 1H), 9.39 (d, J ¼ 7.1 Hz, 1H).
4.3.5. 1-Dodecyl-2-methylpyridinium iodide (12)
To an ethanol solution (80 mL) of 1-alkyl-2-methylpyridinium
halides 8e13 (8 mmol) were added 4-(diethylamino)benzaldehyde
14 (14.2 g, 8 mmol) and piperidine (a few drops). The mixture was
refluxed for 3 days. After the reaction was completed, the reaction
mixture was concentrated. The product was purified by column
chromatography (SiO2, MeOHeCHCl3) to afford orange to red solid.
Yield 85%; mp 120e121 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 0.88
(t, J ¼ 7.3 Hz, 3H),1.20e1.50 (m,18H),1.95 (quin, J ¼ 7.3 Hz, 2H), 3.00
(s, 3H), 4.81 (t, J ¼ 7.3 Hz, 2H), 7.90 (t, J ¼ 7.7 Hz, 1H), 8.00 (d,
J ¼ 7.7 Hz, 1H), 8.48 (t, J ¼ 7.7 Hz, 1H), 9.43 (d, J ¼ 7.7 Hz, 1H).
4.3.6. 2-Methyl-1-octadecylpyridinium iodide (13)
Yield 92%; mp 130e131 ꢂC; 1H NMR (400 MHz, CDCl3)
4.4.1. 2-[4-(Diethylamino)styryl]-1-methylpyridinium iodide (15)
d
¼ 0.88 (t, J ¼ 7.4 Hz, 3H), 1.20e1.50 (m, 30H), 1.95 (quin,
Yield 73%; mp 228e229 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 1.20
J ¼ 7.4 Hz, 2H), 3.01 (s, 3H), 4.81 (t, J ¼ 7.4 Hz, 2H), 8.02 (t,
J ¼ 6.8 Hz, 1H), 8.10 (d, J ¼ 6.8 Hz, 1H), 8.51 (t, J ¼ 6.8 Hz, 1H),
9.88 (d, J ¼ 6.8 Hz, 1H).
(t, J ¼ 7.1 Hz, 6H), 3.48 (q, J ¼ 7.1 Hz, 4H), 4.32 (s, 3H), 6.75 (d,
J ¼ 9.3 Hz, 2H), 7.14 (d, J ¼ 15.6 Hz, 1H), 7.57 (t, J ¼ 7.0 Hz, 1H), 7.64
(d, J ¼ 9.3 Hz, 2H), 7.82 (d, J ¼ 15.6 Hz, 1H), 8.24 (t, J ¼ 7.0 Hz, 1H),

922
M. Matsui et al. / Dyes and Pigments 99 (2013) 916e923
8.34 (d, J ¼ 7.0 Hz, 1H), 8.56 (d, J ¼ 7.0 Hz, 1H); 13C NMR (100 MHz,
IR (KBr)
n
¼ 2922, 1590, 1557, 1525, 1193; Anal. calcd for C35H57IN2:
~
CDCl3)
d
¼ 12.6 (2C), 44.7 (2C), 47.2, 108.3, 111.6 (2C), 121.2, 122.8,
C, 66.44; H, 9.08; N, 4.43%. Found: C, 66.16; H, 8.91; N, 4.03%.
~
123.7, 131.7 (2C), 142.8, 145.6, 145.8, 150.7, 154.0; IR (KBr)
n
¼ 1593,
1160, 1526, 1193; Anal. calcd for C18H23IN2: C, 54.83; H, 5.88; N,
7.10%. Found: C, 54.41, H, 5.75, N, 7.07%.
4.5. Synthesis of 1-alkyl-2-[4-(diethylamino)styryl]pyridinium dyes
25e33
4.4.2. 2-[4-(Diethylamino)styryl]-1-ethylpyridinium bromide (16)
To a watereacetone (2:1) mixed solution (30 mL) of 1-alkyl-2-[4-
(diethylamino)styryl]pyridinium halides 15e20 (1 mmol) was added
a lithium salt 21e24 (1.25 mmol) at ambient temperature. The
mixture was stirred for 1 day. After the reaction was completed, the
mixture was concentrated. The product was purified by column
chromatography (Al2O3, THF/MeOH ¼ 5/1) to provide orange to red
solid or liquid.
Yield 27%; mp 195e196 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 1.22 (t,
J ¼ 7.2 Hz, 6H), 1.64 (t, J ¼ 7.2 Hz, 3H), 3.44 (q, J ¼ 7.2 Hz, 4H), 5.03 (q,
J ¼ 7.2 Hz, 2H), 6.69 (d, J ¼ 8.9 Hz, 2H), 7.02 (d, J ¼ 15.4 Hz, 1H), 7.59
(d, J ¼ 8.9 Hz, 2H), 7.63 (t, J ¼ 7.2 Hz,1H), 7.64 (d, J ¼ 15.4 Hz, 1H), 8.17
(d, J ¼ 7.2 Hz, 1H), 8.20 (t, J ¼ 7.2 Hz, 1H), 8.52 (d, J ¼ 7.2 Hz, 1H); 13
C
NMR (100 MHz, CDCl3)
(2C), 121.2, 123.4, 131.3 (2C), 143.0, 145.0, 145.4, 145.5, 150.4, 152.8; IR
d
¼ 12.5 (2C), 15.6, 44.6 (2C), 53.6, 108.2, 111.4
~
(KBr)
n
¼ 1590, 1160, 1526, 1194; Anal. calcd for C19H25BrN2: C, 63.16;
4.5.1. 2-[4-(Diethylamino)styryl]-1-methylpyridinium
bis(perfluorobutylsulfonyl)imide (25)
H, 6.97; N, 7.75%. Found: C, 63.48, H, 7.24, N, 7.45%.
Yield 80%; 1H NMR (400 MHz, CDCl3)
d
¼ 1.21 (t, J ¼ 7.1 Hz, 6H),
4.4.3. 1-Butyl-2-[4-(diethylamino)styryl]pyridinium bromide (17)
3.34 (q, J ¼ 7.1 Hz, 4H), 4.26 (s, 3H), 6.67 (d, J ¼ 8.9 Hz, 2H), 6.89 (d,
J ¼ 15.6 Hz,1H), 7.47 (t, J ¼ 6.8 Hz,1H), 7.53 (d, J ¼ 8.9 Hz, 2H), 7.58 (d,
J ¼ 15.6 Hz, 1H), 8.07 (t, J ¼ 6.8 Hz,1H), 8.10 (d, J ¼ 6.8 Hz,1H), 8.46 (d,
Yield 71%; 1H NMR (400 MHz, CDCl3)
d
¼ 0.98 (t, J ¼ 7.6 Hz, 3H),
1.22 (t, J ¼ 7.2 Hz, 6H),1.54 (sex, J ¼ 7.6 Hz, 2H),1.95 (quin, J ¼ 7.6 Hz,
2H), 3.44 (q, J ¼ 7.2 Hz, 4H), 5.00 (t, J ¼ 7.6 Hz, 2H), 6.70 (d,
J ¼ 9.2 Hz, 2H), 6.97 (d, J ¼ 15.1 Hz, 1H), 7.62 (t, J ¼ 7.2 Hz, 1H), 7.64
(d, J ¼ 9.2 Hz, 2H), 7.84 (d, J ¼ 15.1 Hz, 1H), 8.08 (d, J ¼ 7.2 Hz, 1H),
8.15 (t, J ¼ 7.2 Hz, 1H), 9.69 (d, J ¼ 7.2 Hz, 1H); 13C NMR (100 MHz,
J ¼ 6.8 Hz, 1H); 19F NMR (376 MHz, CDCl3, ext. CFCl3)
d
¼ ꢀ125.8
~
n
(4F), ꢀ121.0 (4F), ꢀ112.7 (4F), ꢀ80.7 (6F); IR (KBr) ¼ 1592, 1562,
1526,1365,1228,1194, 1177, 1155; Anal. calcd for C26H23F18N3O4S2: C,
36.84; H, 2.74; N, 4.96%. Found: C, 36.54; H, 2.93; N, 4.95%.
CDCl3)
d
¼ 12.6 (2C), 13.7, 19.5, 32.0, 44.7 (2C), 57.8, 108.4, 111.5 (2C),
121.4, 123.1, 124.6, 131.3 (2C), 143.3, 145.3, 145.5, 150.4, 152.9; IR
4.5.2. 2-[4-(Diethylamino)styryl]-1-ethylpyridinium
~
(KBr)
n
¼ 1590, 1155, 1525, 1190; Anal. calcd for C21H29BrN2: C,
bis(perfluorobutylsulfonyl)imide (26)
64.78; H, 7.51; N, 7.19%. Found: C, 64.48; H, 7.24; N, 7.45%.
Yield 61%; 1H NMR (400 MHz, CDCl3)
d
¼ 1.23 (t, J ¼ 7.2 Hz, 6H),
1.61 (t, J ¼ 7.3 Hz, 3H), 3.45 (q, J ¼ 7.2 Hz, 4H), 4.66 (q, J ¼ 7.3 Hz, 2H),
6.69 (d, J ¼ 8.7 Hz, 2H), 6.91 (d, J ¼ 15.6 Hz, 1H), 7.53 (d, J ¼ 8.7 Hz,
2H), 7.56 (t, J ¼ 6.9 Hz, 1H), 7.59 (d, J ¼ 15.6 Hz, 1H), 8.08 (d,
J ¼ 6.9 Hz, 1H), 8.14 (t, J ¼ 6.9 Hz, 1H), 8.57 (d, J ¼ 6.9 Hz, 1H); 19F
4.4.4. 2-[4-(Diethylamino)styryl]-1-octylpyridinium iodide (18)
Yield 75%; mp 173e175 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 0.83 (t,
J ¼ 7.6 Hz, 3H), 1.10e1.50 (m, 16H), 1.91 (quin, J ¼ 7.6 Hz, 2H), 3.42 (q,
J ¼ 7.2 Hz, 4H), 4.83 (t, J ¼ 7.6 Hz, 2H), 6.63 (d, J ¼ 8.9 Hz, 2H), 6.94 (d,
J ¼ 15.6 Hz, 1H), 7.58 (d, J ¼ 8.9 Hz, 2H), 7.60 (d, J ¼ 6.4 Hz, 1H), 7.70
(d, J ¼ 15.6 Hz, 1H), 8.23 (t, J ¼ 6.4 Hz,1H), 8.27 (t, J ¼ 6.4 Hz,1H), 9.12
NMR (376 MHz, CDCl3, ext. CFCl3)
d
¼ ꢀ125.8 (4F), ꢀ120.9
¼ 1591, 1560, 1526, 1355,
~
(4F), ꢀ112.7 (4F), ꢀ80.7 (6F); IR (KBr)
n
1236, 1190, 1154; Anal. calcd for C27H25F18N3O4S2: C, 37.64; H, 2.92;
N, 4.88%. Found: C, 37.33; H, 3.06; N, 4.89%.
(d, J ¼ 6.4 Hz,1H); 13C NMR (100 MHz, CDCl3)
¼ 12.6 (2C),14.0, 22.4,
d
26.0, 28.9, 29.0, 29.8, 31.6, 44.6 (2C), 58.2, 108.1, 111.4 (2C), 121.2,
123.0, 124.6, 131.3 (2C), 143.1, 144.7, 145.4, 150.3, 152.8; IR (KBr)
4.5.3. 1-Butyl-2-[4-(diethylamino)styryl]pyridinium
~
n
¼ 1591,1156,1522,1191; Anal. calcd for C25H37IN2: C, 60.97; H, 7.57;
trifluoromethanesulfonate (27)
N, 5.69%. Found: C, 60.59; H, 7.74; N, 5.60%.
Yield 87%; 1H NMR (400 MHz, CDCl3)
d
¼ 1.01 (t, J ¼ 7.5 Hz, 3H),
1.23 (t, J ¼ 7.1 Hz, 6H), 1.47 (sex, J ¼ 7.5 Hz, 2H), 1.92 (quin, J ¼ 7.5 Hz,
2H), 3.45 (q, J ¼ 7.1 Hz, 4H), 4.58 (t, J ¼ 7.5 Hz, 2H), 6.70 (d, J ¼ 9.2 Hz,
2H), 6.88 (d, J ¼ 15.6 Hz, 1H), 7.50 (d, J ¼ 9.2 Hz, 2H), 7.56 (t,
J ¼ 7.1 Hz, 1H), 7.59 (d, J ¼ 15.6 Hz, 1H), 8.07 (d, J ¼ 7.1 Hz, 1H), 8.14
(t, J ¼ 7.1 Hz, 1H), 8.54 (d, J ¼ 7.1 Hz, 1H); 19F NMR (376 MHz, CDCl3,
~
4.4.5. 2-[4-(Diethylamino)styryl]-1-dodecylpyridinium iodide (19)
Yield 87%; mp 270e271 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 0.85
(t, J ¼ 7.6 Hz, 3H), 0.98 (t, J ¼ 7.3 Hz, 6H), 1.11e1.65 (m, 18H), 1.91
(quin, J ¼ 7.6 Hz, 2H), 3.35 (q, J ¼ 7.3 Hz, 4H), 4.55 (t, J ¼ 7.6 Hz, 2H),
6.65 (d, J ¼ 8.9 Hz, 2H), 6.85 (d, J ¼ 15.6 Hz, 1H), 7.49 (d, J ¼ 8.9 Hz,
2H), 7.54 (d, J ¼ 6.0 Hz, 1H), 7.59 (d, J ¼ 15.6 Hz, 1H), 7.54 (t,
J ¼ 6.0 Hz, 1H), 8.10 (t, J ¼ 6.0 Hz, 1H), 8.50 (d, J ¼ 6.0 Hz, 1H); 13C
ext. CFCl3)
d
¼ ꢀ78.1 (3F); IR (KBr) ¼ 1594, 1564, 1526, 1272, 1263,
n
1031; Anal. calcd for C22H29F3N2O3S: C, 57.63; H, 6.37; N, 6.11%.
Found: C, 57.39; H, 6.12; N, 6.26%.
NMR (100 MHz, CDCl3)
29.0, 29.2, 29.4, 29.8, 31.7, 44.3, 44.5 (2C), 58.3, 108.1, 111.4 (2C),
d
¼ 12.5 (2C), 14.0, 21.6, 22.0, 22.5, 26.0,
4.5.4. 1-Butyl-2-[4-(diethylamino)styryl]pyridinium
121.1, 123.1, 124.6, 131.3 (2C), 143.1, 144.5, 145.4, 150.3, 152.9; IR
bis(trifluoromethylsulfonyl)imide (28)
(KBr)
n
¼ 1590, 1156, 1524, 1190; Anal. calcd for C29H45IN2: C, 63.49;
Yield 76%; 1H NMR (400 MHz, CDCl3)
d
¼ 1.01 (t, J ¼ 7.5 Hz, 3H),
~
H, 8.27; I, 23.13; N, 5.11%. Found: C, 63.18, H, 8.06; N, 5.26%.
1.23 (t, J ¼ 7.1 Hz, 6H), 1.47 (sex, J ¼ 7.5 Hz, 2H), 1.92 (quin, J ¼ 7.5 Hz,
2H), 3.45 (q, J ¼ 7.1 Hz, 4H), 4.58 (t, J ¼ 7.5 Hz, 2H), 6.70 (d, J ¼ 9.2 Hz,
2H), 6.88 (d, J ¼ 15.6 Hz, 1H), 7.50 (d, J ¼ 9.2 Hz, 2H), 7.58 (t,
J ¼ 7.0 Hz, 1H), 7.58 (d, J ¼ 15.6 Hz, 1H), 8.07 (d, J ¼ 7.0 Hz, 1H), 8.14
(t, J ¼ 7.0 Hz, 1H), 8.55 (d, J ¼ 7.0 Hz, 1H); 19F NMR (376 MHz, CDCl3,
~
4.4.6. 2-[4-(Diethylamino)styryl]-1-octadecylpyridinium iodide
(20)
Yield 72%; mp 183e184 ꢂC; 1H NMR (400 MHz, CDCl3)
d
¼ 0.87
(t, J ¼ 7.2 Hz, 3H), 1.19e1.36 (m, 34H), 1.45 (quin, J ¼ 7.2 Hz, 2H), 1.92
(quin, J ¼ 7.2 Hz, 2H), 3.43 (q, J ¼ 7.0 Hz, 4H), 4.84 (t, J ¼ 7.2 Hz, 2H),
6.67 (d, J ¼ 8.7 Hz, 2H), 6.97 (d, J ¼ 15.1 Hz, 1H), 7.60 (t, J ¼ 7.3 Hz,
1H), 7.65 (d, J ¼ 8.7 Hz, 2H), 7.80 (d, J ¼ 15.1 Hz, 1H), 8.29 (t,
ext. CFCl3)
d
¼ ꢀ78.6 (6F); IR (KBr) ¼ 1591, 1560, 1527, 1354, 1203,
n
1191; Anal. calcd for C23H29F6N3O4S2: C, 46.85; H, 4.96; N, 7.13%.
Found: C, 46.67; H, 4.88; N, 7.18%.
J ¼ 7.3 Hz, 1H), 8.39 (d, J ¼ 7.3 Hz, 1H), 9.09 (d, J ¼ 7.3 Hz, 1H); 13
C
4.5.5. 1-Butyl-2-[4-(diethylamino)styryl]pyridinium 4,4,5,5,6,6-
NMR (100 MHz, CDCl3)
d
¼ 12.1, 14.2, 22.7 (2C), 26.2, 29.2, 29.4 (2C),
hexafluorodihydro-4H-1,3,2-dithiazine 1,1,3,3,-tetraoxide (29)
29.6, 29.7 (2C), 29.8 (5C), 30.0, 32.0 (2C), 44.8 (2C), 58.4, 108.3, 111.6
(2C), 121.4, 123.1, 124.9, 131.6 (2C), 143.2, 144.8, 145.6, 150.5, 153.0;
Yield 97%; 1H NMR (400 MHz, CDCl3)
d
¼ 1.01 (t, J ¼ 7.5 Hz, 3H),
1.23 (t, J ¼ 7.1 Hz, 6H), 1.47 (sex, J ¼ 7.5 Hz, 2H), 1.92 (quin, J ¼ 7.5 Hz,

M. Matsui et al. / Dyes and Pigments 99 (2013) 916e923
923
2H), 3.45 (q, J ¼ 7.1 Hz, 4H), 4.57 (t, J ¼ 7.5 Hz, 2H), 6.70 (d, J ¼ 8.9 Hz,
2H), 6.88 (d, J ¼ 15.6 Hz, 1H), 7.51 (d, J ¼ 8.9 Hz, 2H), 7.56 (t,
J ¼ 7.0 Hz, 1H), 7.58 (d, J ¼ 15.6 Hz, 1H), 8.08 (d, J ¼ 7.0 Hz, 1H), 8.14
(t, J ¼ 7.0 Hz, 1H), 8.48 (d, J ¼ 7.0 Hz, 1H); 19F NMR (376 MHz, CDCl3,
~
cif. CCDC 929916 (17), CCDC 929917 (25), and CCDC 929915 (30).
Crystal data for 17: C21H29BrN2, Mw ¼ 389.37, triclinic, P-1, Z ¼ 2,
ꢀ
a ¼ 10.003(4), b ¼ 10.396(4), c ¼ 11.409(4) A,
a
¼ 62.753(11),
b
¼ 73.534(16),
F(000) ¼ 408,
4478 unique (Rint
g
¼ 90.52(2)ꢂ, Dcalcd ¼ 1.296 g cmꢀ3, T ¼ 296 K,
ext. CFCl3)
d
¼ ꢀ127.6 (2F), ꢀ121.1 (4F); IR (KBr)
n
¼ 1591, 1560,
m
¼ 2.064 mmꢀ1, 8268 reflections were corrected,
1526, 1358, 1193, 1155; Anal. calcd for C24H29F6N3O4S2: C, 47.91; H,
4.86; N, 6.98%. Found: C, 47.54; H, 4.75; N, 6.88%.
¼ 0.0276), 220 parameters, R1 ¼ 0.1254,
wR2 ¼ 0.3794, GOF 1.627, refinement on F2. Crystal data for 25:
C26H23F18N3O4S2, Mw
¼
847.58, monoclinic, P21/n,
Z
¼
4,
¼ 92.410(16)ꢂ,
ꢀ
b
4.5.6. 1-Butyl-2-[4-(diethylamino)styryl]pyridinium
bis(perfluorobutylsulfonyl)imide (30)
a ¼ 10.605(12), b ¼ 11.547(13), c ¼ 28.59(3) A,
Dcalcd ¼ 1.609 g cmꢀ3, T ¼ 293 K, F(000) ¼ 1704,
m
¼ 2.8480 cmꢀ1
,
Yield 80%; 1H NMR (400 MHz, CDCl3)
d
¼ 1.00 (t, J ¼ 7.4 Hz, 3H),
32,349 reflections were corrected, 8052 unique (Rint ¼ 0.0503), 677
1.22 (t, J ¼ 7.1 Hz, 6H), 1.47 (sex, J ¼ 7.4 Hz, 2H), 1.90 (quin, J ¼ 7.4 Hz,
2H), 3.45 (q, J ¼ 7.1 Hz, 4H), 4.58 (t, J ¼ 7.4 Hz, 2H), 6.70 (d, J ¼ 9.2 Hz,
2H), 6.88 (d, J ¼ 15.6 Hz, 1H), 7.50 (d, J ¼ 9.2 Hz, 2H), 7.56 (t,
J ¼ 7.2 Hz, 1H), 7.57 (d, J ¼ 15.6 Hz, 1H), 8.07 (d, J ¼ 7.2 Hz, 1H), 8.13
(t, J ¼ 7.2 Hz, 1H), 8.55 (d, J ¼ 7.2 Hz, 1H); 19F NMR (376 MHz, CDCl3,
parameters, R1 ¼ 0.0961, wR2 ¼ 0.3317, GOF 1.051, refinement on F2.
Crystal data for 30: C29H29F18N3O4S2, Mw ¼ 889.67, triclinic, Pꢀ1,
ꢀ
Z ¼ 2, a ¼ 11.450(5), b ¼ 13.101(5), c ¼ 14.163 A,
a
¼ 62.914(11),
b
¼ 75.447(15),
g
¼ 85.904(17)ꢂ, Dcalcd ¼ 1.616 g cmꢀ3, T ¼ 296 K,
F(000) ¼ 900,
m
¼ 0.277 mmꢀ1, 14,849 reflections were corrected,
ext. CFCl3)
d
¼ ꢀ125.9 (4F), ꢀ121.0 (4F), ꢀ112.8 (4F), ꢀ80.7 (6F); IR
8286 unique (Rint ¼ 0.0364), 647 parameters, R1 ¼ 0.0810,
(KBr) v 1591, 1560, 1528, 1360, 1237, 1192, 1168 cmꢀ1; IR:
n
¼ 1560,
wR2 ¼ 0.1229, GOF 1.167, refinement on F2.
~
1522, 1507, 1362, 1355, 1239, 1198; Anal. calcd for C29H29F18N3O4S2:
C, 39.15; H, 3.29; N, 4.72%. Found: C, 39.03; H, 3.33; N, 4.74%.
Appendix A. Supplementary data
4.5.7. 2-[4-(Diethylamino)styryl]-1-octylpyridinium
bis(perfluorobutylsulfonyl)imide (31)
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2013.07.026.
Yield 91%; 1H NMR (400 MHz, CDCl3)
d
¼ 0.86 (t, J ¼ 7.6 Hz, 3H),
1.10e1.53 (m, 16H), 1.96 (quin, J ¼ 7.6 Hz, 2H), 3.45 (q, J ¼ 7.2 Hz,
4H), 5.01 (t, J ¼ 7.6 Hz, 2H), 6.70 (d, J ¼ 8.9 Hz, 2H), 6.98 (d,
J ¼ 15.6 Hz, 1H), 7.54 (d, J ¼ 8.9 Hz, 2H), 7.58 (d, J ¼ 6.4 Hz, 1H), 7.67
(d, J ¼ 15.6 Hz,1H), 8.10 (t, J ¼ 6.4 Hz,1H), 8.18 (t, J ¼ 6.4 Hz,1H), 9.76
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(d, J ¼ 6.4 Hz, 1H); 19F NMR (376 MHz, CDCl3, ext. CFCl3)
d
¼ 125.8
~
n
(4F), ꢀ121.9 (4F), ꢀ112.7 (4F), ꢀ80.7 (6F); IR (KBr)
¼ 1560, 1522,
1507, 1362, 1355, 1239, 1198; Anal. calcd for C33H37F18N3O4S2: C,
41.92; H, 3.94; N, 4.44%. Found: C, 42.20; H, 4.12; N, 4.10%.
4.5.8. 2-[4-(Diethylamino)styryl]-1-dodecylpyridinium
bis(perfluorobutylsulfonyl)imide (32)
Yield 88%; 1H NMR (400 MHz, CDCl3)
d
¼ 0.87 (t, J ¼ 7.2 Hz, 3H),
1.11e1.43 (m, 24H),1.91 (quin, J ¼ 7.6 Hz, 2H), 3.44 (q, J ¼ 7.2 Hz, 4H),
4.56 (t, J ¼ 7.2 Hz, 2H), 6.69 (d, J ¼ 9.2 Hz, 2H), 6.87 (d, J ¼ 15.4 Hz,1H),
7.50 (d, J ¼ 9.2 Hz, 2H), 7.55 (d, J ¼ 6.8 Hz,1H), 7.58 (d, J ¼ 15.4 Hz,1H),
8.11 (t, J ¼ 6.8 Hz, 1H), 8.15 (t, J ¼ 6.8 Hz, 1H), 8.52 (d, J ¼ 6.8 Hz, 1H);
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[7] Wang ZS, Li FY, Huang CH. Highly efficient sensitization of nanocrystalline
TiO2 films with styryl benzothiazolium propylsulfonate. Chem Commun 2000:
2063e4.
19F NMR (376 MHz, CDCl3, ext. CFCl3)
d
¼ ꢀ125.9 (4F), ꢀ121.0
~
(4F), ꢀ112.8 (4F), ꢀ80.7 (6F); IR (KBr)
n
¼ 1592, 1560, 1526, 1357,
1237, 1191, 1154; Anal. calcd for C37H45F18N3O4S2: C, 44.36; H, 4.53;
N, 4.19%. Found: C, 44.37; H, 4.46; N, 4.21%.
[8] Tulyakova E, Delbaere S, Fedorov Y, Jonusauskas G, Moiseeva A, Fedorova O.
Multimodal metal cation sensing with bis(macrocylic) dye. Chem Eur
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2011;17:10752e62.
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styryl dyes. Biophys J 1988;53:665e70.
[12] Lee CC, Hu AT. Synthesis and optical recordeing properties of some novel
styryl dyes for DVD-R. Dyes Pigm 2003;59:63e9.
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for free radical polymerization. Dyes Pigm 2008;77:510e4.
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sulfate aggregates. J Photohem Photobiol A Chem 1999;121:63e73.
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Chem Int Ed 2010;49:7444e7.
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4.5.9. 2-[4-(Diethylamino)styryl]-1-octadecylpyridinium
bis(perfluorobutylsulfonyl)imide (33)
Yield 68%; 1H NMR (400 MHz, CDCl3)
d
¼ 0.88 (t, J ¼ 7.3 Hz, 3H),
1.21e1.42 (m, 36H), 1.92 (quin, J ¼ 7.3 Hz, 2H), 3.45 (q, J ¼ 7.0 Hz,
4H), 4.56 (t, J ¼ 7.3 Hz, 2H), 6.69 (d, J ¼ 8.7 Hz, 2H), 6.88 (d,
J ¼ 15.6 Hz, 1H), 7.50 (d, J ¼ 8.7 Hz, 2H), 7.56 (d, J ¼ 6.8 Hz, 1H), 7.58
(d, J ¼ 15.6 Hz, 1H), 8.08 (d, J ¼ 6.8 Hz, 1H), 8.15 (t, J ¼ 6.8 Hz, 1H),
8.54 (d, J ¼ 6.8 Hz, 1H); 19F NMR (376 MHz, CDCl3, ext. CFCl3)
d
~
n
¼ ꢀ125.8 (4F), ꢀ120.9 (4F), ꢀ112.7 (4F), ꢀ80.7 (6F); IR (KBr)
¼ 2927, 1590, 1560, 1527, 1355, 1237, 1154; Anal. calcd for
43H57F18N3O4S2: C, 47.55; H, 5.29; N, 3.87%. Found: C, 47.47; H,
C
5.16; N, 3.83%.
4.6. Single X-ray crystallography of 17, 25, and 30
Single crystals were obtained by diffusion method using
dichloromethane and hexane. The structure was solved by direct
methods and refined by fill-matrix least-squares calculations.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Cetre via www.ccdc.cam.ac.uk/data_request/