ISSN 0036-0244, Russian Journal of Physical Chemistry, 2006, Vol. 80, No. 3, pp. 453–460. © Pleiades Publishing, Inc.

, 2006.
Original Russian Text © A.V. Vannikov, A.D. Grishina, Yu.G. Gorbunova, Yu.Yu. Enakieva, T.V. Krivenko, V.V. Savel’ev, A.Yu. Tsivadze, 2006, published in Zhurnal Fizicheskoi
Khimii, 2006, Vol. 80, No. 3, pp. 537–544.

PHOTOCHEMISTRY
AND MAGNETOCHEMISTRY

Photorefractive IR-Spectrum Composites Prepared from

Polyimide and Ruthenium(II) Tetra-15-crown-5-phthalocyaninate
with Axially Coordinated Triethylenediamine Molecules
A. V. Vannikov, A. D. Grishina, Yu. G. Gorbunova, Yu. Yu. Enakieva, T. V. Krivenko,
V. V. Savel’ev, and A. Yu. Tsivadze
Frumkin Institute of Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 117071 Russia
E-mail: van@elchem.ac.ru
Received February 21, 2005

Abstract—It is established that supramolecular ensembles on the basis of the complex of ruthenium(II) with
tetra-15-crown-5-phthalocyanine and axially coordinated triethylenediamine molecules ((R4Pc)Ru(TED)2,
where R4Pc2– and TED denote 4,5,4',5',4'',5'',4''',5'''-tetraksis-(1,4,7,10,13-pentaoxatridecamethylene)phthalo-
cyaninate ion and triethylenediamine molecule, respectively) make an aromatic polyamide layer photoelectri-
cally sensitive to 1064-nm Nd : YAG laser radiation, exhibit third-order susceptibility, and, consequently, impart
photorefractive properties to the polymer layer at this wavelength.
DOI: 10.1134/S0036024406030253

The photorefractive (PR) effect consists in the forma- by two crossed laser beams. In the present work, we exam-
tion (in the recording layer) of a phase hologram shifted ined the photoelectric, nonlinear optical, and photorefrac-
somewhat with respect to the interference pattern formed tive properties of an aromatic polyimide (API),

O O
C O C
N N N
C C n

O O
(API)

doped with a complex of ruthenium(II) with tetra-15- ylenediamine, (R4Pc)Ru(TED)2. The structure of the
crown-5-phthalocyanine and axially coordinated trieth- complex was determined by XRD analysis [1]:

N( 4A)
O(4)
O(3)
O(2)
O(9A)

O(8A) O(5)
N( 3A)
O(10A) N( 6) O(1)
O(6A)
Ru(1)
N(1) N(5A) O(7)
N(2) N(2A)
O(7A) N(5) N(1A)
O(6)

O(7A) N(6A)
N(3) O(10)

O(8)
O(5A)
O(2A)
O(9)
N(4)
O(3A)
O(4A)

453
454 VANNIKOV et al.

I2(0) the bright interference bands. A consequence of such a

φ (‡)
shift is an enhancement in the intensity of the beam
I1(0) propagating from the interference band to the diffrac-
2θ
x tion lattice (signal beam) at the expense of a weakening
of the second (pumping) beam.
– –
– 2 PR materials can find a variety of practical applica-
+ + tions [2], especially in amplifying information-carrying
– – –
beams. Such materials can also be used for recording
+ + + – 1 holograms of moving objects, since polymer materials
– – with a short delete–record time (on the order of several
E0 +
+ + 2 milliseconds) can be synthesized [2–6].
+
The authors of [7] proposed a PR-based method for
Esc −ψ medical diagnostics of living organisms. Biological tis-
sues are known to strongly scatter radiation over the
I2(L) I2(L) entire visible spectrum, being, however, relatively
transparent in the near IR region. A pulse from a femto-
second laser was passed through a tissue. To diagnose a
(b) tissue, it is necessary to separate the scattered radiation
I
from the regular (nonscattered) one, which carries
information on the characteristics of this tissue. For this
purpose, a delay of the scattered radiation (by making
its optical path longer) with respect to the regular radi-
Λ ation in the signal beam is used. The hologram in the
PR layer is formed only because of the interaction of
the regular component of the signal beam with the
pumping beam, since the scattered radiation reaches the
–Ψ PR layer after the pumping pulse has passed. Hologram
reconstruction is performed using the standard optical
scheme.
x In the present work, we recorded a diffraction lat-
tice, the simplest hologram in a polymer layer. The
measuring cell is displayed in Fig. 1a. Two crossing
Esc, beams (schematically shown by arrows), ~3 mm in
∆n
diameter each, create an interference pattern in polymer
layer 1. In the region of bright interference bands (the
solid lines inside the layer in Fig. 1a), electron–hole
pairs are generated. Under the action of the applied
field E0, charges with different signs move in the
applied field E0 in opposite directions, being gradually
captured by traps. For the PR effect to arise, the charges
Fig. 1. (a) Cell for measuring the PR characteristics of a of different signs should differently shift prior to be
polymer layer and the pattern of the diffraction lattice in it: captured by traps. In most available PR polymer mate-
(1) the polymer layer and (2) ITO (In2O3 : Sné2) electrodes
deposited onto glass supports (the slanted solid lines repre- rials, holes are more mobile than electrons, traveling,
sent bright interference bands, while the dashed lines depict therefore, over longer distances from the interference
the diffraction lattice; trapped electrons are denoted by the band. Figure 1a schematically shows that electrons are
plus sign, while holes, by the minus sign; see the text); (b) trapped in the region of bright interference bands, while
the distributions of the light intensity (upper curve), electric
field strength Esc, and refractive index modulation ∆n holes, experiencing the action of the field E0, travel into
(lower curve) at a phase shift of the diffraction lattice with dark interference bands. When separated, the electrons
respect to the interference band of –30°. and holes form a periodic space charge distribution,
which, in turn, gives rise to a periodic field Esc directed
perpendicular to the interference bands (along the x axis).
Recent studies have demonstrated that the most As can be seen from Fig. 1a, the predominant motion of
promising materials for the realization of the PR effect holes along the direction of the field E0, makes the max-
are polymer layers possessing electron-transport prop- imum of the field Esc shift by a phase –ψ relative to the
erties and photoelectric sensitivity and containing chro- bright interference band. When the polarity of the elec-
mophores that impart electric susceptibility to the trodes (and, hence, the direction of E0) is changed,
material. In this case, two interfering laser beams give holes move upwards (Fig. 1a), causing the phase shift
rise to a phase diffraction lattice shifted with respect to to switch from –ψ to +ψ and changing the direction of

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY Vol. 80 No. 3 2006

 PHOTOREFRACTIVE IR-SPECTRUM COMPOSITES PREPARED FROM POLYIMIDE
energy transfer from one beam to another to the
opposite.
The polarization of chromophores with nonlinear
optical properties in the total periodic field E tot = E sc +
E 0 results in the modulation of the refractive index, ∆n,
i.e., in the formation of a diffraction lattice with a phase
coinciding with that of the field Esc. Indeed, in the pres-
ence of an electric field E, the well-known relationship
between the refractive index and the linear electric sus-
ceptibility, n2 = 1 + 4πχ(1), can be recast as n2(E) = 1 +
(1)
4π[ χ ( E ) + E(χ(2) + χ(3)E)], an expression that contains
(1)
the nonlinear terms χ(2)E + χ(3)E2 ( χ ( E ) is the linear sus-
ceptibility in the presence of the field E; χ(2) and χ(3) are
second- and third-order susceptibilities, respectively).
Combining with the static field E0, the periodic field Esc
produced by the space charge yields the modulated
total field E tot , which, in turn, modulates the refractive
index: ∆n = [n2(Etot) – n2(E0)]/[n(Etot) + n(E0)]. Since
∆n
n and n(Etot) + n(E0) ≈ 2n, substituting Etot and E0
in the above formula for n2(E) yields
(1)
∆n = (2π/n)[ χ Esc + Esc(χ(2) + χ(3)(2E0 + Esc)].
Films cast from a solution and then dried are char-
acterized by a random orientation of the functional
dopants, including nonlinear optical chromophores.
For such layers, the first- and second-order susceptibil-
ities are equal to zero. It is reasonable to assume that, in
solid polyimide layers with a glass-transition tempera-
ture of ~240°ë, the reorientation of the chromophores
under the action of the field E0 and, consequently, the
formation of an anisotropic medium with nonzero sus-
ceptibilities is hampered. For the random orientation of
the doping molecules, only the third-order susceptibil-
ity is nonzero; therefore, ∆n = (2π/n)χ(3)Esc(2E0 + Esc).
Typical distributions of the light intensity in the
interference pattern (upper curve) and the field Esc and
the refractive index modulation ∆n at a Esc field phase
shift of ψ = –30° (lower curve) are displayed in Fig. 1b.
The long-wave boundary of API is close to 470 nm;
therefore, only the (R4Pc)Ru(TED)2 complex imparts
photoelectric sensitivity at λ = 1064 nm and third-order
susceptibility successfully to the polymer layer, thereby
specifying its PR properties.
In the present work, we compared the photoelec-
tric and PR properties of the layers, containing
(R4Pc)Ru(TED)2, in the absence of additional dopants,
a situation where triphenylamine units of API play the
role of electron-transport sites, and in the presence of
ferrocene (Fc) in an amount sufficient to allow elec-
trons to migrate by hopping from molecule to molecule
of Fc.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY Vol. 80
455
EXPERIMENTAL
The complex of ruthenium(II) with a tetra-15-
crown-5-phthalocyanine molecule and two axially
coordinated triethylenediamine molecules was synthe-
sized as described in [1]. The composition and purity of
the complex was controlled spectroscopically (elec-
tronic, IR, NMR, and mass spectroscopies).
The layers were cast from a solution of the polymer
composition in tetrachloroethane on glass supports
coated with a conducting In2O3 : SnO2 (ITO) film
(Fig. 1a) and dried at 60°ë. Pure ferrocene in the form
of coarse crystals was obtained by sublimating the
compound at an elevated temperature. The thickness of
the solid polymer layer was ~5 µm. The electronic
absorption spectra of the solid layers were recorded on
a Shimadzu UV-3101PC spectrophotometer.
The photoelectric and PR characteristics were mea-
sured using a Nd : YAG continuous laser (λ = 1064 nm).
When measuring photocurrent, we illuminated the
layer from the side of the ITO transparent film with a
single beam; a layer of an opaque silver paste played
the role of the second electrode.
The nonlinear optical properties were estimated by
measuring the intensity of the second harmonic (λ =
532 nm) generated by the layer when irradiated with a
Nd : YAG pulsed laser with a fundamental wavelength
of 1064 nm in the absence and presence of a static elec-
tric field. When measuring the intensity of the second
harmonic, the ITO electrode was grounded, while the
free surface of the polymer layer was charged with neg-
–
ative species, predominantly CO 3 (from a corona dis-
charge positioned nearby), so as to make its potential
negative. That the 532-nm harmonic appears during
pulsed-laser irradiation (1064 nm) suggests that the
layer contains chromophores with nonlinear optical
properties. The 532-nm radiation was isolated with
the help of optical filters and recorded using a photo-
multiplier and a digital voltmeter. The detection sys-
tem was calibrated against a 5-µm-thick poly(methyl
methacrylate) standard layer doped with 0.5 mol/dm3
of 4-anilino-4'-nitroazobenzene (Disperse Orange
DO-3, a dye with an asymmetrical chromophore;
J0.5 ∝ 6.8 pm/V [8]).
The PR effect was measured by the double-beam
method in the cell shown in Fig. 1a. The fluence rates
of the incident beams 1 and 2 (Fig. 1a) were I1(0) =
I2(0) = 0.14 W/cm2.
RESULTS AND DISCUSSION
The electronic absorption spectra of API layers con-
taining 2.5 and 7.5 wt % (R4Pc)Ru(TED)2 are displayed
in Fig. 2. As can be seen, the long-wave boundary
threshold is positioned at 1400 nm, substantially farther
than that observed in the absence of the dopant
(470 nm). Thus, the electronic absorption of the layers
in the near IR and visible spectra belongs to the
No. 3 2006
456 VANNIKOV et al.

A A 10–6 to 10–4 mol/l, the solutions of the complex were

2.
0.06
2
1 aggregate in the form of so-called “brickwork.” On the
1.
1 that the crystal contains one (R4Pc)Ru(TED)2 mole-
0.02
0 boring molecules (Fig. 3). Note that chloroform mol-
400 600 800 1000 1200 1400
λ, nm
Fig. 2. Electronic absorption spectra of an API layer doped
with (R4Pc)Ru(TED)2 in amounts of (1) 2.5 and (2) 7.5 wt %.
Ru-complex, more specifically to the Q-band associ-
ated with the π π* transition in the tetra-15-crown-
5-phthalocyanine macrocycle. The methods of synthe-
sis and the physicochemical and optical properties of
crown-substituted phthalocyanines of various metals
and their supramolecular structures were examined in
detail in review article [9]. The spectral properties of
complexes of ruthenium with the tetra-15-crown-5-
phthalocyanine molecule and axially coordinated
ligands can be found in [1, 10, 11]. The halfwidth of the
Q-band of (R4Pc)Ru(TED)2 in chloroform at a concen-
tration of 10–4 mol/l was reported to be 820 cm–1
[1, 10], which means that the complex exists in the
monomeric form. Over a concentration range of from
found to obey the Beer–Lambert–Bourguer law. The
exciton interaction model described in [12] explains
the broadening and bathochromic shift of the Q-band
of the complex by the formation of a supramolecular
other hand, in [1], (R4Pc)Ru(TED)2 monocrystals
were grown and the structure of the (R4Pc)Ru(TED)2
complex was established using XRD analysis. Note
cule per two solvate chloroform molecules, which are
located between the crown ether fragments of neigh-
ecules influence the conformation of crown ethers,
ordering them in the form of brickwork.
We recorded the diffuse reflection spectrum of
(R4Pc)Ru(TED)2 · 7CHCl3 monocrystals and found that
the Q-band has a halfwidth of 4000 cm–1; i.e., it is sub-
stantially broader than that observed in solution. In
addition, a band near 900 nm appeared. These effects
can be explained by the brickwork-type arrangement of
the molecules in the crystal. By analogy, it is reasonable
to attribute the broadening of the Q-band and the
appearance of detectable absorption in the near IR
region in the 7.5 wt % (R4Pc)Ru(TED)2 –API compos-
ite (Fig. 2) to the formation of brickwork-type
supramolecular structures.
Photoelectric Properties
The field dependence of the photocurrent jph(E0) for
the 7.5 wt % (R4Pc)Ru(TED)2–API composite were
measured in the absence and presence of ferrocene.

Fig. 3. A fragment of the structure of the (R4Pc)Ru(TED)2 · 7CHCl3 crystal.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY Vol. 80 No. 3 2006

 PHOTOREFRACTIVE IR-SPECTRUM COMPOSITES PREPARED FROM POLYIMIDE 457

ϕ × 107 ϕ × 108 Imide

–2.0
2 3
2 1
–1.5
2

1 –1.0
1
–0.5

1064 nm
0 100 200
E0, V/ µm 0

Fig. 4. Quantum efficiency of the formation of mobile

charge carriers as a function of the strength of the static
electric field applied for the 7.5 wt % (R4Pc)Ru(TED)2–
API composite in the (1) absence and (2) presence of fer-
rocene.
Figure 4 shows how the quantum efficiency of the for-
mation of mobile charge carriers depends on the
strength E0 of the electric field applied. The quantum
efficiency was calculated by the formula
ϕ(E0) = jph(E0)hc/eλ[I0(1 – 10–A(1064))],
where hc/λ = 1.165 eV is the energy of a 1064-nm
photon, I0 = 5.2 W/cm2 is the fluence rate, and (1 –
10–A(1064)) is radiant energy absorbed in the layer.
In the absence of additives, mobile charge carriers
in API are holes, with triphenylamine (TPA) units of
API acting as transport sites [5, 6]. The presence of
(R4Pc)Ru(TED)2 makes the layers under study sensi-
tive to 1064-nm radiation:
1064 nm
(R4Pc)Ru(TED)2 [(R4Pc)Ru(TED)2]*.
At low (R4Pc)Ru(TED)2 concentrations, the photoge-
neration and the transport of holes can be described by
the scheme
íPÄ + [ ( R 4 Pc )Ru ( TED ) 2 ]*
+ . – .
íPÄ + ( R 4 Pc )Ru ( TED ) 2 , ( ∆G ),
+ . + .
íPÄ + íPÄ íPÄ + íPÄ etc. (hop-
ping-type hole transport).
Here, ∆G is the Gibbs energy of transfer of an elec-
tron from the ground-state level of the TPA molecule to
the lowest half-occupied level of the electronically
excited complex (process (2)). Figure 4 shows that the
introduction of 20 wt % Fc results in a nearly tenfold
increase in the quantum efficiency of formation of
mobile holes.
That the quantum efficiency of formation of holes in
the absence of Fc is low can be explained by the fact
0.5 e 0.38 Ç
e Fc
∆G 0.56 V
((R4Pc)Ru(TED)2 complex)*
1.0 0.76 V
TPA
E red-ox1/2, V
Fig. 5. Relative positions of the ground-state levels of the
TPA and imide fragments of API, ferrocene, and
(R4Pc)Ru(TED)2; ∆G is the Gibbs energy of transfer of an
(1) electron from the transport site to the lowest excited level of
the photoexcited (R4Pc)Ru(TED)2 complex.
that the Gibbs energy of transfer of an electron from a
TPA molecule to an excited (R2Pc)Ru(TED)2 molecule
is characterized by a positive change in the Gibbs
energy. Indeed, the ground-state energy of the TPA
molecule corresponds to the equilibrium potential of
oxidation of TPA of 0.76 V (with respect to a calomel
electrode), while the equilibrium potential of reduction
of an excited (R4Pc)Ru(TED)2 molecule is close to its
equilibrium potential of oxidation, 0.56 V, by analogy
with the (R4Pc)Ru(CO)(CH3OH) complex [11]. Thus,
the Gibbs energy of transfer of an electron from the
ground-state level of the TPA molecule to the half-
occupied level of the excited complex is ∆G ~ +0.2 eV
(2) (Fig. 5). When Fc is introduced (with an equilibrium
oxidation potential of 0.38 V), mobile holes (Fc+) are
formed due to the transfer of an electron,
[ ( R 2 Pc )Ru ( TED ) 2 ]* + Fc
(3)
– . + .
[ ( R 2 Pc )Ru ( TED ) 2 ] + Fc ,
followed by the transport of holes by means of hopping
of electrons from Fc molecule to Fc molecule,
+ . + .
Fc + Fc Fc + Fc etc.
The phototransfer of an electron by reaction (3) is ener-
getically more favorable than that by reaction (2), since,

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY Vol. 80 No. 3 2006

458
I2.1/I2.0 (‡)
1.018
γ0
1.012
1.006
1.000
0 10 20
Fig. 6. Time evolution of the relative intensity of beam 2 at the exit of the measuring cell upon switching-on and switching-off of
beam 1 (the upward and downward arrows, respectively). The structure of the measuring cell is displayed in Fig. 1a. The thickness
of the polymer composite layer was 5 µm. The fluence rates of the beams were I1(0) = I2(0) = 0.14 W/cm2. The strength of the static
electric field applied was 57 V/µm. Curves (a) and (b) were measured with the electric field directed as shown in Fig. 1a and in the
opposite direction, respectively.
as shown in Fig. 5, it is characterized by a negative
Gibbs energy change, ∆G ~ –0.18 eV.
Thus, the introduction of (R4Pc)Ru(TED)2 com-
plexes into an API layer makes it photosensitive at λ =
1064 nm. The quantum efficiency of formation of
mobile holes depends on the Gibbs energy of transfer of
an electron from the ground-state level of the transport
site to the photoexcited complex of ruthenium.
Nonlinear Optical Properties
To study the nonlinear optical properties of API
layers doped with (R4Pc)Ru(TED)2 (7.5 wt %), we
measured the characteristics of the generation of the
second harmonic. The intensity of second-harmonic
radiation is related to the second- and third-order elec-
tric susceptibilities as
J0.5 ∝ (χ(2) + χ(3)E0).
When the nonlinear chromophores are randomly
distributed over the sample, the second-order suscepti-
bility, χ(2) = Nβ〈cos3ξ〉, equals zero, since 〈cos3ξ〉 = 0
(N is the concentration of chromophores; β is the sec-
ond-order molecular polarizability; and ξ is the angle
between the principal axis of the chromophore and a
given direction, for example, the normal to the surface
of the layer; and the angle brackets denote averaging).
API layers without dopants do not generate the second
harmonic. It was found that API layers doped with
(R4Pc)Ru(TED)2 generate the second harmonic only
in the presence of a static field with strength E0. A
comparison with a reference yielded χ(2) + χ(3)E0 =
7.4 pm/V.
Thus, (R4Pc)Ru(TED)2 determines the nonlinear
optical properties of the composite. Since the randomly
orientated chromophores in the API matrix cannot
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY
VANNIKOV et al.
(b) t, s
0 10 20 30
1.000
0.994
0.988
0.982
30 I2.1/I2.0
t, s
change their orientation at room temperature (for API,
Tg ~ 240°ë), the second-order susceptibility equals
zero; i.e., only the third-order susceptibility is responsi-
ble for the generation of the second harmonic. That the
second harmonic intensity decays slowly after the
corona discharge is switched off can be explained by
the long time it takes for the negative species at the sur-
face (deposited from the corona) to discharge. The dark
halftime τ1/2 = 12 s of decay of the surface potential is
determined by the conductivity σ of the layer: τ1/2 =
(8.85 × 10–14εln2)/σ (ε is the dielectric constant of the
layer).
Thus, API layers doped with (R4Pc)Ru(TED)2
exhibit photoelectric sensitivity at 1064 nm and nonlin-
ear optical behavior, factors that may impart PR prop-
erties to these systems.
(4) Photorefractive Characteristics
The arrangement of the unit for measuring PR prop-
erties depicted in Fig. 1a is characterized by a Q-factor
of Q = 2πLλ/Λ2n = 4.8 (L = d/cosφ is the length of the
optical path along the bisectrix of the angle between the
beams (d = 5 µm); at λ = 1064 nm, θ = 15°, and n ~ 1.5,
the space pattern period equals Λ [=λ/2nsin(θ/2)] =
2548.6 nm. It is known [13] that a Q-factor value close
to 5 corresponds to Bragg diffraction rather than
Raman–Nutt diffraction.
We measured the time evolution of the relative
intensity of the second beam passed through an API
layer doped with (R4Pc)Ru(TED)2 and Fc at various
polarities of the static electric field E0 (Fig. 6). The
measurements were performed as follows: at t = 0,
beam 2 was switched on and its intensity I2, 0 at the exit
from the cell was measured; then, the field E0 was
applied, which, however, produced no effect on the
intensity of beam 2. Several seconds later, beam 1 was
Vol. 80 No. 3 2006
 PHOTOREFRACTIVE IR-SPECTRUM COMPOSITES PREPARED FROM POLYIMIDE
switched on (indicated by the upward arrow; the inten-
sity of beam 2 during the action of beam 1 is denoted
by I2, 1). As a result, the intensity of beam 2 increased
(Fig. 6a) or decreased (Fig. 6b), depending on whether
the potential of the lower (exit) electrolyte (Fig. 1a) was
negative or positive. That the curves are asymmetrical
is unambiguously indicative of the PR effect; this
behavior can be explained by the reversal of the drift of
holes compared to that shown in Fig. 1a. As a result, a
diffraction lattice shifted to the right of the interference
bands (by a phase +ψ rather than –ψ) is formed. Under
these conditions, the intensity of beam 1 increases at
the expense of that of beam 2.
The growth of the relative intensity of beam 2 in
Fig. 6a can be described by the equation (the solid
approximating line)
I2, 1/I2, 0 = 1 + (γ0 – 1){1 – EXP[–(t – t0)/τ]}, (5)
where γ0 = I2, 1/I2, 0 at the plateau (Fig. 6a) and τ is the
time of response of the composite to the switching-on
of beam 1 (the characteristic time of formation of the
PR diffraction lattice). The approximating line (Fig. 6a)
was plotted at γ0 = 1.016 and τ = 2 s. If the intensities
of the incident beams are equal, I1(0) = I2(0), (Fig. 1a),
the gain coefficient is given by [14]
Γ = ln[γ0/(2 – γ0)]/L, (6)
where L = d/cos(φ – θ) is the length of the optical path
of beam 2 in the layer.
As can be seen from Fig. 7a, the gain coefficient
increases with the strength E0 of the applied static field.
In the absence of additional dopants, the API–
(R4Pc)Ru(TED)2 composition is characterized by a low
gain coefficient, which becomes equal to the absorption
coefficient (α = 37 cm–1; the dashed line in Fig. 7a) only
at a static field strength of ~105 V/µm. At E0 =
125 V/µm, the net gain coefficient, Γ – α, is 12.5 cm–1.
As E0 increases from 100 to 125 V/µm, the characteris-
tic time of formation of the diffraction lattice decreases
from 4 to 3 s. We believe that the low value of Γ and the
long response time can be explained by a low quantum
efficiency of the formation of mobile charge carriers
(Fig. 4). Indeed, the rate of formation of the diffraction
lattice, ∂(∆n)/∂t, is related to ϕ(E0) (formula (1)) as [13]
∂ ( ∆n )/∂t ∼ ∂E sc /∂t ∼ ∂N cc /∂t
–A(λ)
(7)
= [ ϕ ( E 0 )I 0 ( 1 – 10 )/hν ] – N cc /t cc ,
where Ncc and tcc are the concentration and lifetime of
photogenerated mobile charge carriers.
As can be seen from Fig. 7, in the presence of fer-
rocene, Γ = 40 and 140 cm–1 at E0 = 37 and 110 V/µm,
respectively. As a result, the difference Γ – α is rather
large, attaining 103 cm–1 at E0 = 110 V/µm. As E0
increases from 25 to 110 V/µm, the characteristic time
of formation of the diffraction lattice decreases from
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY Vol. 80
459
Γ, Òm–1
150
(‡) 2 (b)
τ, s
1
100
2
3
50 1
1
0
40 80 100 0 50 100
E0, V/ µm E0, V/ µm
Fig. 7. (a) Double-beam gain coefficient Γ and (b) the char-
acteristic time τ of formation of the diffraction lattice for the
(1) API–(R4Pc)Ru(TED)2 and (2) (R4Pc)Ru(TED)2–Fc
composite layers.
3.4 to 0.1 s, in agreement with formula (7), which pre-
dicts that ∂(∆n)/∂t should increase with ϕ(E0) (Fig. 4).
Thus, we found that supramolecular ensembles
formed by (R4Pc)Ru(TED)2 (1) sensitize the photoelec-
tric sensitivity of polymer layers to Nd : YAG laser radi-
ation (1064 nm), (2) exhibit third-order susceptibility,
and, as a consequence, (3) impart PR properties to poly-
mer layers.
The quantum efficiency of the formation of mobile
charge carriers is determined by the Gibbs energy of
transfer of an electron from the ground-state level of the
transport site to the photoexcited (R4Pc)Ru(TED)2
complex. In the presence of Fc molecules, which
take over the transport of charge carriers from API
triphenylamine units, this quantity increases by an
order of magnitude due to a decrease in ∆G from
+0.2 eV to ~–0.18 eV. As a result, at E0 = 110 V/µm,
the double-beam gain coefficient increases from ~40 to
140 cm–1 while the characteristic time of formation of
the diffraction lattice decreases from ~3.5 to ~0.1 s.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research (project nos. 04-03-08051, 05-03-
33206, and 05-03-32984) and by the International Sci-
entific Technological Center (project no. 2207).
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