ISSN 0030400X, Optics and Spectroscopy, 2012, Vol. 112, No. 3, pp. 443452. Pleiades Publishing, Ltd., 2012.

Original Russian Text I.A. Vasileva, N.A. Voitova, R.N. Nurmukhametov, 2012, published in Optika i Spektroskopiya, 2012, Vol. 112, No. 3, pp. 488497.

CONDENSEDMATTER
SPECTROSCOPY

Effect of the Fluorine Substitution in Ethyl Groups

of 1,4Distyrylbenzene on the Fine Structure Fluorescence
and Fluorescence Excitation Spectra
I. A. Vasilevaa, N. A. Voitovaa, and R. N. Nurmukhametovb
a

Moscow State Pedagogical University, Moscow, 119992 Russia

State Scientific Center of the Russian Federation Karpov Institute of Physical Chemistry, Moscow, 105064 Russia
email: irina.vasilieval@gmail.com
Received July 12, 2011

AbstractThe finestructure fluorescence and fluorescence excitation spectra of conjugated chain com
pounds, 1,4distyrylbenzene (DSB) and its fluorinesubstituted derivative ,1,4distyrylbenzene, have
been obtained by the Shpolskii method in an noctane matrix at a temperature of 4.2 K. These spectra have
been simulated by representing the band of each of the vibronic transitions as the sum of a zerophonon line
and a phonon wing with the corresponding parameters, such as the halfwidths of the spectral lines and the
DebyeWaller factors. Based on this simulation, the relative intensities of vibronic transitions have been
determined and the frequencies of normal vibrations in the S0 and S1* states have been refined. It has been
found that the energy of the purely electronic transition in the molecule of the fluorinesubstituted derivative
is higher by 950 cm1 compared to the unsubstituted DSB. The parameters of the FranckCondon and
HerzbergTeller interactions have been determined. The observed violation of the mirror symmetry between
the conjugated spectra is explained by the interference of intramolecular interactions.
DOI: 10.1134/S0030400X12020269

INTRODUCTION
Among compounds with complex polyatomic mol
ecules, hydrocarbons that contain systems of bonds
(especially, aromatic hydrocarbons) are the most stud
ied by the methods of electronic absorption and lumi
nescence spectroscopy. Much less attention has been
paid to fluorinesubstituted derivatives of hydrocar
bons, including fluorocarbon polymers. The question
of how the fluorine substitution in hydrocarbons
affects their electronic spectra still has not been suffi
ciently studied.
It was revealed that some of the fluorocarbons or
fluorinesubstituted derivatives of aromatic hydrocar
bons possess valuable applied properties. Among these
compounds are highly chemically stable fluoroplas
tics, such as polytetrafluorethylene (also known as
Teflon), fluorocarbon electrolytes in chemical current
sources [1], medicinal substances, including blood
substitutes such as Perftoran [2], and so on.
Analysis of the literature on the spectral properties
of fluorinated conjugated compounds showed that,
even on broadband absorption and fluorescence spec
tra of this group of compounds, data are scarce. In
studies of ,difluorosubstituted derivatives of stil
bene and diphenylbutadiene [35], it was noted that,
upon fluorine substitution, the absorption and fluores
cence band maxima are hypsochromically shifted by
10 and 30 nm, respectively.

There are also works [68] that report data on the

maxima positions in broadband absorption and fluo
rescence spectra of room temperature solutions of
DSB derivatives in which some H atoms of benzene
rings were replaced with F atoms. In this case, no reg
ularities in the shifts of absorption and fluorescence
spectra in relation to the number of fluorine atoms
have been observed.
To our knowledge, fine structure spectra of fluo
rinesubstituted derivatives of conjugated com
pounds have not been studied.
The objective of this work was to investigate how
the replacement of H atoms at double bonds of the
hydrocarbon molecule by F atoms affects the fine
structure vibronic spectra of the molecule using 1,4
distyrylbenzene and ,tetrafluorodistyrylbenzene
as an example. The structural formulas of the com
pounds under study are shown below.

443

DSB,

1,4distyrylbenzene;

444

VASILEVA et al.

rather intense continuous background, which made it

impossible to determine the integral intensity of each
vibronic band directly from the experimental spectra
with the accuracy necessary for the analysis. This dif
ficulty was surmounted by applying the previously
developed method of simulation of conjugated spectra
[11]. The simulated spectrum is a series of vibronic
bands, each of which is a sum of a narrow zero
phonon line that is described by the Lorentz function
and a broad phonon wing that is described by the
Gauss function. In order for the simulated spectrum to
be coincided with the experimental spectrum, it is
necessary to select the widths and the spacing between
the maxima of the zerophonon line and the phonon
wing and the value of the DebyeWaller factor. This
method was already used in studies of fine structure
spectra of some organic chainlike phosphors [12, 13].

Optical density
0.2

0.1

0
250

350

450
Wavelength, nm

DISCUSSION OF RESULTS

Fig. 1. Absorption spectra of (1) DSB and (2) FDSB at

room temperature.

At room temperature, the absorption and fluores

cence spectra of DSB and FDSB consist of broad
bands, which exhibit rough vibrational structure
(Fig. 1). From comparison of the wavelengths of the
absorption and fluorescence band maxima (Table 1), it
follows that the substitution of H atoms in ethylene
bonds of the DSB molecule for F atoms causes a hyp
sochromic shift of bands. This unusual substitution
effect of H atoms at double bonds for F atoms is simi
lar to the aforementioned effect for substituted deriva
tives of stilbene and diphenylbutadiene; i.e., it is char
acteristic of F atoms attached to the double carbon
bond.
Fine structure fluorescence and fluorescence exci
tation spectra of the compounds under study mea
sured in nhexane matrices at 4.2 K are shown in
Figs. 2 and 3. It can be seen that there is a certain vio
lation of the mirror symmetry between the conjugated
spectra of both DSB and FDSB. From the analysis of
these fine structure spectra, we determined the posi
tions of the resonance 00 bands and calculated the
changes in the energy of the purely electronic transi
tion that were caused by the fluorine substitution
(Table 2).
The vibronic bands in the conjugated spectra of
DSB and FDSB manifest themselves in the frequency
ranges up to 3382 and 4830 cm1, respectively. The
intensities of the vibronic bands that correspond to
high frequencies, which are overtones or combinations

F
F
FDSB.

F
F

,tetrafluorodistyrylbenzene.
EXPERIMENTAL
We measured the conjugated fluorescence and
absorption spectra of DSB and FDSB at room tem
perature in a solution in a polar solvent, dichlo
romethane ( = 1.55 D). Results of the investigation
of the spectral properties of DSB and FDSB mole
cules [9, 10] show that the degree of resolution of the
vibronic structure and the shape of the conjugated flu
orescence and fluorescence excitation spectra are sen
sitive to the choice of the solvent, concentration of
their solutions, cooling temperature, and the rate of
freezing. The fine structure of the spectra of these
compounds was resolved most fully in nhexane at
4.2 K and at a concentration of solutions of 5
10 5 M/L or lower. The quasiline structure in conju
gated spectra of DSB was resolved much better than in
the spectra of its fluorinesubstituted analog. In the
spectra of both compounds, it is observed against a
Table 1
DSB

, nm

FDSB
absorption

fluorescence
max, nm

max, nm

413

355

absorption

fluorescence
max, nm

max,

fluorescence
max, nm

absorption
max, nm

55167

393

341

56610

20

14

OPTICS AND SPECTROSCOPY

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2012

2293
2547

1610
1747
1959

869
996
1181
1330

1008
852
650

304

1360
1188

1740
1895

2193

3195
2936
2780
2609

641

1600

536

I I
11

445

00
153
336

152
00

EFFECT OF THE FLUORINE SUBSTITUTION

00

00
22

23

24

25

26

26

27

28
v 103, cm1

1566

Fig. 2. Fluorescence and fluorescence excitation spectra and integral intensities of vibronic bands of DSB in nhexane at C = 5
105 M/L and 4.2 K. The spectra were corrected for the sensitivity of the setup.

1705

2318

4014

4830

3275

1695
696

1249

1 1

00
135

00

154

1021

1333
1182

2846

4392

4792

3225

0 0
22

23

24

25

0 0
27 26

26

27

28

29

30

31
32
v 103, cm1

Fig. 3. Fluorescence and fluorescence excitation spectra and integral intensities of vibronic bands of FDSB in nhexane at C =
5 105 M/L and 4.2 K. The spectra were corrected for the sensitivity of the setup.

of frequencies of normal vibrations, are low and are

not observed in experimental spectra. To perform
detailed comparative analysis of vibronic transitions
and determine their quantitative characteristics, we
simulated the spectra. By selecting the necessary
parameters we were able to reach a nearly total coinci
dence between the experimental and simulated spec
OPTICS AND SPECTROSCOPY

Vol. 112

No. 3

2012

tra. This result was obtained for the following parame

ters: the widths of the zerophonon line for both com
pounds were 20 cm1, the widths of the phonon wings
were 120 cm1, and the DebyeWaller factor was 0.15.
The discrepancy in the shortwavelength range of the
fluorescence excitation spectrum is seemingly related
to the fact that the model does not take into account

446

VASILEVA et al.

Table 2
DSB
00 , cm1
Fluorescence:
25610 5
Fluorescence excitation:
25609 5

00 , nm (S
390.48
390.48

FDSB
00 , cm1

S0), eV
3.18

Fluorescence:
26560 5
Fluorescence excitation:
26567 5

an increase in the intensity in this range due to the

scattering. Therefore, it became clear that the back
ground against which vibronic peaks manifest them
selves is caused by the intense phonon wing rather than
by the inhomogeneous broadening. A large width and
a considerable intensity of phonon wings are indicative
of a strong electronphonon interaction of impurity
molecules of the compounds under study with the sur
rounding medium. In addition, in the course of simu
lation, we refined the positions of closely located
vibronic bands.
The relative integral intensities of vibronic bands
that were obtained as a result of simulation of the spec
tra are shown by vertical lines in Figs. 2 and 3. The
spectra would have this shape if vibronic bands did not
have phonon wings.
It can be seen from the data of Table 3 that the
replacement of hydrogen atoms at double bonds by F
atoms does not lead to marked changes in the frequen
cies of the main normal vibrations active in the conju
gated spectra of DSB. Upon passage from DSB to
FDSB, the intensity in the spectra of the latter is
somewhat redistributed, which manifests itself as an
increase in the intensity of bands in the range 1330
1700 cm1. At the same time, the relative intensity of
the vibronic band with a frequency of 985(989) cm1
in FDSB is approximately half that of the band at
1008(996) cm1 in the DSB molecule. The frequencies
of the excited state are given in the parentheses. The
conjugated spectra of both compounds show mirror
asymmetry with respect to frequencies, which mani
fests itself in that the bands that are observed in one of
the conjugated spectra are absent in the other spec
trum. Thus, for the FDSB molecule, the bands caused
by vibrations with the frequencies 1454 and 1486 cm1
are observed only in the fluorescence excitation spec
trum, whereas, in the DSB molecule, the vibration
1448 cm1 is observed only in the fluorescence spec
trum, while the bands caused by the vibration with the
frequency 1484 cm1 occur in the two conjugated
spectra.
The performed analysis allowed us to calculate the
parameters of intramolecular interactions, which are
presented in Tables 3 and 4. For the DSB and FDSB
molecules, these parameters were calculated for 32
and 25 normal vibrations, respectively.

00 , nm (S
376.5

S0), eV
3.30

, eV
0.12

376.41

For all these vibrations, which are active in the

spectra, the parameters a/2 and are nonzero, which
indicates that the vibronic transitions are affected by
both intramolecular interactions. For the overwhelm
ing majority of vibrations in the two molecules, the
FCfactor prevails, while the influence Herzberg
Teller interaction manifests itself in the violation of the
mirror symmetry in the intensity distribution over the
conjugated spectra.
The modern theory is capable of calculating the
exact values of the HTparameters only for molecules
of the D2h and C2v symmetry, because, for them, at a
specified vibronic frequency, the two vectors that are
determined by the FC and HTinteractions and
determine the vector of the transition dipole moment
are collinear [13, 14]. In our case, the symmetry of
molecules of the two examined compounds is lower
and each vector caused by the HTinteraction over a
certain totally symmetric normal coordinate lies in the
plane of the molecule but may have different direc
tions for different vibrations. Therefore, the actual
value of the HTparameter may prove to be greater
than the found value.
CONCLUSIONS
In this work, using 1,4distyrylbenzene and ,
1,4distyrylbenzene as an example, we showed that, as
in the case of compounds with a related structure, such
as stilbene and diphenylbutadiene, the replacement of
H atoms at double bonds by F atoms causes a hypso
chromic shift of the fluorescence and absorption
bands. From the fine structure spectra, we revealed
that the frequency of the purely electronic transition in
the molecule of the fluorinesubstituted derivative is
shifted toward the shortwavelength range by approxi
mately the same value. From this, it follows that the
effect of the hypsochromic shift does not depend on
the nature of the solvent. It seems that the main reason
for this shift is related to a violation of the planar struc
ture of the molecule due to an enhancement of steric
effects. It is likely that an increase in the intensity of
bands in the range 13301700 cm1 in the conjugated
fine structure spectra of FDSB can be explained by the
same reason. We simulated the spectra, as a result of
which we obtained the integral intensities of vibronic
bands in the fluorescence and fluorescence excitation
spectra of the two compounds. A combined analysis of
OPTICS AND SPECTROSCOPY

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2012

EFFECT OF THE FLUORINE SUBSTITUTION

447

Table 3. Characteristics of vibronic bands and calculated parameters of the intramolecular interaction for the 1,4distyrylben
zene molecule
Fluorescence

Fluorescence excitation
fl

00i ,
cm1
0
33
63
102
132
152
183
204
205
263
264
304
337
366
366
389
410
459
536
626
650
674
732
778
794
825
852
887
944
968
1008
1036
1066
1088
1127
1162
1188
1209
1229
1252

abs

J
interpretation

experiment calculation

1
2
3
4
21
5
6
22
23
7
24
8
9
25
3 + 7
5 + 6
10
26
11
27
3 + 10
28
29
12
6 + 10
13
14
1 + 13
3 + 12
3 + 6 + 10
15
16
210
4 + 14
12 + 23
17
3 + 15
18
19
3 + 210
8 + 13
20

00i ,
cm1

1
0.348
0.163
0.122
0.079
0.681
0.238
0
0
0.059
0
0.208
0.127
0
0
0
0
0.098

0.123
0.078
0.689
0.240
0
0.01
0.058
0
0.233
0.130
0.03
0.01
0.01
0
0.098

0
33
51
90
132
153
172
180
205
292
264
304
336
344
366
389
410
486

0
0
0.063
0

0.01
0
0.063
0.01

536
584
641
681

0
0
0.09
0
0.16
0.068
0.077

0
0
0.09
0
0.16
0.068
0.077

732
778
794
825
869
887
921

0
0.152
0.102
0
0.035

0
0.152
0.102
0
0.035

968
996
1021
1066
1088

0.129
0.103
0.281
0.15
0

0.129
0.103
0.281
0.152
0

1127
1162
1181
1209
1229

0.196

0.194

1265

OPTICS AND SPECTROSCOPY

Parameters

Vol. 112

No. 3

2012

J
interpretation

1
2
3
4
21
5
6
22
23
7
24
8
9
25
3 + 7
5 + 6
10
26
11
27
3 + 10
28
29
12
6 + 10
13
14
1 + 13
3 + 12
3 + 6 + 10
15
16
210
4 + 14
12 + 23
17
3 + 15
18
19
3 + 210
8 + 13
20

experi calcula
ment
tion
1
0
0.559
0.256
0
0.446
0.226
0.03
0.39
0.389
0
0.098
0.54
0
0.373
0.42
0.05
0.366

0.260
0.01
0.449
0.23
0.03
0.384
0.384
0
0.098
0.533
0.027
0.372
0.423
0.05
0.366

0.492
0.056
0.373
0.3

0.49
0.06
0.372
0.29

0.044
0.057
0
0.142
0.222
0
0.059

0.047
0.06
0.01
0.142
0.221
0.01
0.058

0.072
0.108
0.071
0.075
0

0.072
0.109
0.073
0.08
0

0
0.048
0.204
0
0.117

0.01
0.048
0.203
0.01
0.117

0.14

0.137

FC

HT

a/2

0.43
0.08
0.19 0.09
0.75 0.08
0.485 0.005
0.36
0.43

0.26
0.19

0.545

0.185

0.355
0.375

0.255
0.275

0.4

0.3

0.43

0.18

0.2

0.1

0.435
0.035
0.18 0.08

0.36 0.03
0.295 0.025

0.23

0.13

0.49 0.04
0.245 0.145

0.41

0.035

448

VASILEVA et al.

Table 3. (Contd.)
Fluorescence

Fluorescence excitation
fl

00i ,
cm1
1277
1297
1300
1330
1360
1375
1401
1432
1448
1484
1553
1573
1588
1600
1633
1657
1688
1703
1740
1774
1779
1806
1852
1895
1934

2016
2072
2193
2209
2254
2293
2308
2368
2391
2418

abs

J
interpretation

experiment calculation
1 + 18
3 + 17
21
211
22
23
24
25
2 + 21
4 + 20
26
27
28
29
212
30
31
32
24 + 23
4 + 27
213
23 + 7
33
214
3 + 31
5 + 30
6 + 28
13 + 15
28 + 23
30 + 23
7 + 30
11 + 22
10 + 25
215
216
15 + 18
10 + 30
13 + 23
217
10 + 33
13 + 26
218
12 + 30
219

Parameters

00i ,
m1

0.119

0.119

1277

0.175
0
0
0.272
0.117
0.067
0.057

0.176
0
0.01
0.27
0.116
0.068
0.057

1297
1282
1330
1360
1375
1399
1432

0.219
0.136
0.118
0.146
0
0.535
0.24
0.09
0.059

0.221
0.137
0.116
0.144
0
0.533
0.212
0.09
0.059

1448
1479
1525
1569
1588
1610
1633
1668
1688

0.063

0.064

1703

0.275
0
0.135
0

0.27
0
0.135
0.01

1747
1774
1779
1806

0.053

0.053

1852

0.118
0.08

0.118
0.08

1895
1959

0
0
0.052

0.01
0
0.052

1992
2042
2161

0.046
0
0
0.035
0.04
0.042
0

0.046
0
0
0.038
0.039
0.043
0

2209
2254
2293
2308
2368
2391
2418

J
interpretation
1 + 18
3 + 17
21
211
22
23
24
25
2 + 21
4 + 20
26
27
28
29
212
30
31
32
24 + 23
4 + 27
213
23 + 7
33
214
3 + 31
5 + 30
6 + 28
13 + 15
28 + 23
30 + 23
7 + 30
11 + 22
10 + 25
215
216
15 + 18
10 + 30
13 + 23
217
10 + 33
13 + 26
218
12 + 30
219

experi calcula
ment
tion
0.05

0.054

0
0.054
0.22
0
0.133
0.1
0.029

0.01
0.058
0.221
0.01
0.13
0.102
0.031

0
0.106
0.172
0.198
0
0.257
0
0.217
0.044

0.01
0.109
0.168
0.194
0
0.260
0.01
0.221
0.046

0.036

0.037

0.227
0
0
0.179

0.23
0
0
0.18

0.039

0.041

0.023
0.254

0.023
0.254

0
0
0.174

0
0
0.174

0
0
0.117
0
0
0
0

0
0
0.117
0
0.02
0
0

OPTICS AND SPECTROSCOPY

Vol. 112

FC

HT

a/2

0.26

0.16

0.285
0.31
0.35
0.29

0.185
0.21
0.01
0.03

0.285
0.35
0.375
0.41

0.185
0.02
0.035
0.03

0.62
0.295
0.385

0.11
0.195
0.085

0.5

0.02

No. 3

2012

EFFECT OF THE FLUORINE SUBSTITUTION

449

Table 3. (Contd.)
Fluorescence

Fluorescence excitation
fl

00i ,
cm1
2440
2476
2519

2609
2643
2677

2712
2750
2756

2780
2802
2818
2899
2936

2969
2974
3106
3163
3195
3235
3266
3314
3353

3382

abs

J
interpretation

experiment calculation
18 + 20
3 + 10 + 33
14 + 30
16 + 26
220
6 + 10 + 33
13 + 32
12 + 33
221
15 + 30
14 + 33
16 + 30
222
15 + 32
17 + 28
18 + 27
223
17 + 29
224
17 + 31
15 + 33
21 + 26
18 + 30
225
19 + 30
23 + 26
226
21 + 30
18 + 33
21 + 31
26 + 27
227
23 + 30
228
229
29 + 30
230
30 + 31
231
232
2 + 230
1 + 30 + 31
3 + 29 + 31
31 + 33

00i ,
cm1

0.056

0.054

2425

0.053

0.054

2476

0.057

0.057

2547

0.09

0.09

2609

0.07

0.071

2643

0.068

0.068

2689

0.056

0.046

2712

0
0.093

0
0.091

2750
2756

0.146
0
0.11

0.146
0
0.114

2780
2798
2818

0.1

0.101

2899

0.135

0.135

2936

0
0.122
0
0.089

0
0.127
0
0.089

2658
2974
3050
3163

0.136
0.11
0.018
0
0.052

0.136
0.113
0.02
0
0.05

3195
3235
3266
3336
3353

0.063

0.063

3382

OPTICS AND SPECTROSCOPY

Parameters

Vol. 112

No. 3

2012

J
interpretation
18 + 20
3 + 10 + 33
14 + 30
16 + 26
220
6 + 10 + 33
13 + 32
12 + 33
221
15 + 30
14 + 33
16 + 30
222
15 + 32
17 + 28
18 + 27
223
17 + 29
224
17 + 31
15 + 33
21 + 26
18 + 30
225
19 + 30
23 + 26
226
21 + 30
18 + 33
21 + 31
26 + 27
227
23 + 30
228
229
29 + 30
230
30 + 31
231
232
2 + 230
1 + 30 + 31
3 + 29 + 31
31 + 33

experi calcula
ment
tion
0.085

0.085

0.08

0.08

0.022

0.027

0.018

0.018

0.064

0.064

0
0

0
0.025

0
0
0

0.051
0
0

0.046

0
0
0
0

0
0
0.014
0.07

0
0
0
0
0

0.03
0
0
0.023
0

FC

HT

a/2

450

VASILEVA et al.

Table 4. Characteristics of vibronic bands and calculated parameters of the intramolecular interaction for the fluorodistyrylben
zene molecule
Fluorescence

Fluorescence excitation
fl

00i,
cm1
0
64
130
154
211
250
308
422
600
696
750
985
1021
1060
1182
1200
1201
1250
1333
1392
1454
1486
1500
1540
1566
1584
1600
1638
1698
1705
1735
1790
1890
1970
2042
2120
2318
2364
2402
2510

abs

J
interpretation

experiment calculation

1
2
3
21
22
23
4
5
6
7
8
9
10
24
11
12
13
25
14
15
26
16
17
18
19
20
21
22
23
24
25
27
28
29
5 + 19
210
211
212

0.25
0.5
0.633
0.3
0.125
0.13
0.06
0
0.08
0.02
0.1
0.202
0.1
0.239
0
0.24
0.3
0.373
0
0
0
0
0.75
0.85
0.95
0.5
0.7
0.3
0.605
0
0
0
0
0.017
0
0.04
0.02
0.02
0.046

Parameters

0.5
0.64
0.3
0.127
0.134
0.258
0.01
0.078
0.02
0.1
0.203
0.1
0.24
0
0.24
0.3
0.372
0
0.01
0.01
0
0.757
0.846
0.941
0.5
0.706
0.29
0.608
0.01
0.01
0.01
0
0.017
0
0.045
0.02
0.025
0.046

00i,
cm1
0
64
135
154
211
270
308
422
600
696
750
989
1011
1057
1182
1200
1201
1249
1323
1392
1454
1486
1500
1540
1566
1584
1600
1642
1695
1705
1735
1790
1890
1978
2022
2114
2318
2364
2402
2498

J
interpretation

experi calcula
ment
tion
0.094
0.57
0
0.406
0.158
0
0.03
0.081
0.222
0.05
0.03
0.03
0.24
0
0
0.06
0.26
0.03
0.022
0.199
0.06
0
0.06
0
0.1
0.2
0.352
0.33
0
0.2
0.25
0.12
0
0
0.025
0.048
0
0
0.028

0.563
0.01
0.41
0.58
0
0.34
0.078
0.221
0.048
0.029
0.029
0.24
0.01
0
0.058
0.26
0.029
0.022
0.203
0.058
0
0.058
0.01
0.102
0.203
0.348
0.33
0.01
0.203
0.25
0.123
0
0
0.027
0.05
0
0
0.034

OPTICS AND SPECTROSCOPY

Vol. 112

1
2
3
21
22
23
4
5
6
7
8
9
10
24
11
12
13
25
14
15
26
16
17
18
19
20
21
22
23
24
25
27
28
29
5 + 19
210
211
212

FC

HT

a/2

0.73
0.02
0.45 0.35
0.595
0.045

0.19
0.09
0.375
0.095
0.18
0.04
0.245 0.075
0.31 0.14
0.405
0.085
0.295 0.195
0.365 0.125
0.53 0.02
0.39 0.22
0.275
0.17

0.175
0.07

0.555
0.51
0.645
0.58
0.715
0.56
0.44
0.275
0.3
0.225

0.315
0.41
0.325
0.13
0.125
0.015
0.34
0.175
0.2
0.125

No. 3

2012

EFFECT OF THE FLUORINE SUBSTITUTION

451

Table 4. (Contd.)
Fluorescence

Fluorescence excitation
fl

00i ,
cm1
2573
2656
2690
2846
2908
2918
2972
3080
3132
3168
3225
3266
3326
3396
3410
3470
3580
3780
4014

4214
4307

4392

4543
4792
4830

abs

J
interpretation

experiment calculation
7 + 19
8 + 16
213
7 + 21
12 + 14
13 + 16
12 + 19
214
13 + 18
11 + 21
215
216
217
218
219
16 + 22
220
19 + 22
221
222
223
224
225
5 + 19 + 21
12 + 13 + 14
4 + 221
8 + 16 + 20
9 + 218
12 + 14 + 19
9 + 16 + 23
9 + 220
9 + 20 + 22
12 + 16 + 19
12 + 217
10 + 219
13 + 18 + 20
11 + 20 + 21
16 + 17 + 22
22 + 216
12 + 224
14 + 221
20 + 219

00i ,
cm1

0.168
0.168
0.05
0.029

0.168

2573

0.052
0.031

2646
2690

0.363

0.363

1871

0
0.34

0
0.343

2908
2918

0
0.216
0.23
0.35
0.45

0
0.216
0.23
0.349
0.446

2972
3080
3132
3168
3200

0.228
0.26
0.044
0.12
0
0
0
0.013

0.409
0.26
0.044
0.121
0
0
0
0.013

3275
3326
3385
3410
3470
3580
3780
4014

0.12

0.119

4214

0.028

0.028

4307

0.245

0.243

4392

0.21

0.21

4543

0.23

0.231

4792

0.075

0.076

4830

OPTICS AND SPECTROSCOPY

Parameters

Vol. 112

No. 3

2012

J
interpretation
7 + 19
8 + 16
213
7 + 21
12 + 14
13 + 16
12 + 19
214
13 + 18
11 + 21
215
216
217
218
219
16 + 22
220
19 + 22
221
222
223
224
225
5 + 19 + 21
12 + 13 + 14
4 + 221
8 + 16 + 20
9 + 218
12 + 14 + 19
9 + 16 + 23
9 + 220
9 + 20 + 22
12 + 16 + 19
12 + 217
10 + 219
13 + 18 + 20
11 + 20 + 21
16 + 17 + 22
22 + 216
12 + 224
14 + 221
20 + 219

experi calcula
ment
tion
0

0
0.066

0
0.064

0.05

0.051

0.015
0.02

0.015
0.02

0
0
0.012
0
0.017

0
0
0.012
0
0.017

0.29
0
0.054
0
0.015
0.02
0
0.025

0.15
0
0.054
0
0.015
0.022
0
0.024

0.04

0.036

0.02

0.02

0.1

0.021

FC

HT

a/2

452

VASILEVA et al.

the intensities of vibronic transitions in the conjugated

spectra of the examined compounds allowed us to
conclude that the observed mirror asymmetry of the
conjugated spectra is caused by the interference of the
FranckCondon and HerzbergTeller interactions.
In conclusion, we note that investigations of fluor
inated hydrocarbons and carbons by the methods of
ordinary and fine structure spectroscopy is a very
promising direction of basic and applied research.
ACKNOWLEDGMENTS
This work was partially supported by the Ministry
of Education and Science of the Russian Federation in
terms of the Federal Targeted Program Scientific and
ScientificPedagogical Personnel of Innovative Rus
sia (20092013), project no. 16.740.11.0465.
REFERENCES
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Nauk 6 (11), 998 (1997).
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Translated by V. Rogovoi

OPTICS AND SPECTROSCOPY

Vol. 112

No. 3

2012