J. Phys. Chem.

B 2000, 104, 4047-4059 4047

Electrochemical Preparation and EPR Studies of Lithium Phthalocyanine: Evaluation of

the Nucleation and Growth Mechanism and Evidence for Potential-Dependent Phase
Formation

Govindasamy Ilangovan, Jay L. Zweier, and Periannan Kuppusamy*

The EPR Center and DiVision of Cardiology, Department of Medicine, Johns Hopkins UniVersity School of
Medicine, 5501 Hopkins BayView Circle, Baltimore, Maryland 21224
ReceiVed: October 1, 1999

A very reliable and reproducible electrochemical preparative procedure to obtain oxygen-sensitive lithium
phthalocyanine (LiPc) microcrystalline powder, a critical material for in vivo application of electron
paramagnetic resonance (EPR) oximetry to measure the partial pressure of molecular oxygen pO2, is described.
Important issues including the effect of preparative conditions on the resulting material and the influence of
the deposition mechanism on crystal structure are investigated using cyclic voltammetry, chronoamperometry,
X-ray diffraction (XRD), and high- and low-frequency EPR measurements. The electrochemical measurements
reveal that electrodeposition of LiPc follows a nucleation pathway. Detailed electrocrystallization studies
show that the nucleation mechanism is instantaneous and the three-dimensional growth is controlled by the
diffusion of the reactant from the bulk solution. Critical evidence, for deposition potential-dependent
electrochemical phase formation, is presented. The XRD studies indicate that, in certain deposition conditions,
namely, deposition at potentials +0.1 and +0.2 V (Ag/AgCl), the β structure of LiPc, which is insensitive to
molecular oxygen in terms of EPR oximetry, is formed in higher fraction. On the other hand, at deposition
potentials +0.4 and +0.7 V, exclusively the oxygen-sensitive x form is obtained. A rapidity test showed that
while at deposition potentials +0.4 and +0.7 V only the x form is obtained, the +0.4 V sample responds
more quickly to oxygen than the +0.7 V sample. From the present work, a variety of LiPc microparticles,
suitable for in vivo EPR oximetry applications, can be prepared.

Introduction in the oxygen-sensitive x form.3f The oxygen-insensitive R and

Lithium phthalocyanine (LiPc), an intrinsic semiconductor,
has been found to be a useful electron paramagnetic resonance
(EPR) oximetry probe for in vivo biological applications.1 The
EPR oximetry technique has been demonstrated to provide
accurate and reproducible measurements of local concentrations
of molecular oxygen in a variety of biological tissues including
brain,1a tumor,1d and heart.1b,c However, synthesis of LiPc in
the pure and desirable oxygen-sensitive form has been a critical
problem and challenge in this field.2 This monomolecular
organic semiconductor shows polymorphism, and depending
upon the preparation condition, it can crystallize in three
different structures, namely, the oxygen-sensitive x form, the
commonly obtained R form, or the relatively rare β form.
Critical changes in their magnetic behavior are observed for
these polymorphs due to their very different crystal structures.
Detailed EPR studies3 of these three polymorphs have demon-
strated very different magnetic properties that strongly correlate
with the nature of molecular packing. Apart from its potential
use as an oximetry probe, LiPc has aroused fundamental interest
because of its interesting electrical4 and magnetic behavior.3
The EPR oximetry technique is based on the principle of
Heisenberg spin-spin exchange between the triplet-state mo-
lecular oxygen and spin probes. Among the three known
polymorphs of LiPc, such a spin-spin exchange is reported only
* To whom correspondence should be addressed. E-mail:kuppu@
welch.jhu.edu. Phone: (410) 550-3229. Fax: (410) 550-2448.
10.1021/jp9935182 CCC: $19.00 © 2000 American Chemical Society
Published on Web 04/05/2000
β structures of LiPc show a monoclinic unit cell with parameters
a ) 2.57 nm, b ) 0.38 nm, c ) 2.36 nm, and β ) 91.0° and
the space group C2/c3a and a ) 1.94 nm, b ) 0.49 nm, c )
1.40 nm, and β ) 120.36° and the space group P21/c,
respectively.3e However, the x form shows a tetragonal unit cell
with parameters a ) b ) 1.385 nm and c ) 0.65 nm and the
space group P4/mcc.3e Thus, fundamental structural differences
make the x polymorph behave differently from the other two.
A notable difference among the three forms is seen in the form
of large variations in the EPR signal line width. The line width
of the x form has been reported to be extremely narrow, about
26 mG in a high vacuum, while the other two forms exhibit
line widths of about 200 and 400 mG, respectively.3g Although
it is not completely understood yet why the x form gives such
a narrow EPR line compared to the other two forms, the oxygen-
broadening effect, which is seen only in the x form, has been
understood in terms of crystal structure. Figure 1 illustrates unit
cells projected on the stacking axis, which is defined as the c
axis in the case of the x polymorph and the b axis in the case
of the R and β forms. It is clear from Figure 1 that the tetragonal
structure of the x form has microchannels of width about 6 Å
since the molecular packing is straight.3a,e,f,j But in the cases of
R and β structures, the molecular packing is tilted to some angle
(91.0° for R and 120.36° for β structures), and hence these
channels are narrowed and partially blocked.3f Thus, oxygen
molecules (size 2.8 × 3.9 A2) can easily diffuse into the channels
of the x form and hence can perturb spin diffusion along the
4048 J. Phys. Chem. B, Vol. 104, No. 17, 2000
Figure 1. Molecular structure and crystallographic packing of LiPc:
(top, left) molecular structure, (top, right) crystallographic packing of
LiPc, (bottom) schematic illustration of molecular stacking in LiPc along
the stacking axis. An octahedral microchannel is formed between the
four stacks in the x form since the packing is straight with a channel
bore size of 6 Å. This channel is narrowed in the R and β forms due
to a tilt in the packing [after ref 3a,e,f,j].
stacking axis via Heisenberg spin exchange. There is no such
possibility for oxygen penetration in the other two forms. As a
consequence, the small oxygen effect observed in the case of
the other polymorphs is only a surface effect, which is virtually
negligible.3f These observations reveal that optimization of the
synthetic procedure is very critical to selectively obtain the
oxygen-sensitive LiPc, which is required for biological oxim-
etry.1 Moreover, the synthetic method should yield bulk material
unlike the thin films extensively reported in prior studies.3
Though this one-dimensional semiconducting solid has been
synthesized and characterized as thin films mainly by the vapor
deposition method3 and a few electrochemical deposition
methods,2b,3g,h there has been no systematic investigation on the
electrochemical preparation of the oxygen-sensitive x form of
LiPc crystalline powder. It is very important to optimize the
deposition conditions and investigate the fundamental charac-
teristics of phase formation to obtain and control desired oxygen
sensitivity in the LiPc crystals. It is well-known that the
deposition potential is the single most critical parameter
(assuming that the other factors, namely, migration, convection,
or diffusion, that are associated with transport phenomena are
avoided by continuous stirring of the solution during electrolysis)
in any electrodeposition to get the desired crystal structure, size,
spatial density, and surface texture of the resulting particles.
For example, deposition of any low-dimensional molecular
solids such as tetrathiofulvalene complexes has resulted in
simultaneous growth of different phases with different stoichi-
ometries during electrocrystallization at different potentials.5
The present work was initiated with the following goals: (i)
Optimization of the electrochemical preparation of the x form
of LiPc by the potentiostatic method where the charge-transfer
process can be controlled precisely, unlike the galvanostatic
method used previously,6 so that the preparation method is more
reliable and reproducible. The galvanostatic deposition method
Ilangovan et al.
is associated with some experimentally uncontrollable param-
eters. For example, the applied voltage is varied without the
experimenter’s control, and any undesired high voltages induced
at the electrode due to concentration polarization can result in
overoxidation and decomposition, leading to different product
compositions at different experimental times. (ii) Extensive
characterization of the LiPc obtained in various deposition
potentials using X-ray diffraction (XRD) and EPR line-shape
analysis so that the individual contributions of the various forms
can be evaluated and quantified. This analysis should enable
one to choose the right material for a given application. (iii)
Evaluation of the LiPc as an EPR oximetry probe for in vivo
biological applications. This comprehensive investigation com-
prising electrochemical synthesis, fundamental characterization,
and applications for EPR oximetry should enable solution of
some of the fundamental problems in the preparation and use
of this material.
Experimental Details
Electrochemical Synthesis and Current-Time Transient
Measurements. All the electrochemical measurements were
carried out in dry acetonitrile (Aldrich, HPLC grade) with a
CHI electrochemical analyzer controlled by a personal computer
(PC). The conventional three-electrode setup was used. In the
chronoamperometric and cyclic voltammetric (CV) studies, a
platinum (Pt) disk with geometric area 0.07 cm2 was used after
its surface was cleaned with dilute nitric acid. A Ag/AgCl
reversible redox couple was used as the reference electrode.
The Pt working electrode (BAS, West Lafayette, IN) was not
subjected to any special electrochemical pretreatment except
washing it with dilute nitric acid (0.1 M) and deionized water
successively, since electrochemical pretreatment complicates the
electron-transfer event at the electrode-solution interface.7
Further, the geometric area of the working electrode was used
in all the quantitative calculations, and it was assumed to be
equal to the electrochemical area since the Pt surface appeared
very smooth and correspondingly the roughness factor was
expected to be close to unity. A Pt foil was used as the auxiliary
electrode, and the ratio of the geometric area between the counter
and working electrodes was more than 100, so that activation
overpotential is minimized. An excess concentration of tetra-
butylammonium perchlorate (TBAP) (ICN Biochemicals,
Aurora, OH) was used as the supporting electrolyte. Digitized
chronoamperometric (i-t) transients at 50 ms intervals were
further analyzed through the commercial Sigma Plot software
(SPSS, Chicago, IL) to evaluate the nucleation and growth
mechanism.
For bulk electrochemical synthesis of LiPc, a bigger platinum
mesh electrode with very high surface area (BAS, West
Lafayette, IN) was used as the working electrode in a large-
volume electrolysis cell. The electrochemical cell setup and
electrolysis procedure were similar to those described by
Afeworki et al.2b Briefly, to 100 mL of acetonitrile containing
0.1 M TBAP was added 200 mg of Li2Pc with constant stirring
so that all Li2Pc added was completely dissolved. The resultant
dark blue solution was transferred to one of the two compart-
ments of the cell. A Pt wire with relatively less surface area
was used as the counter electrode in the second compartment,
which was connected to the main working electrode compart-
ment through a fritted disk. The reference electrode was inserted
into the working electrode compartment directly. During
electrolysis, no special effort was used to thermostat the cell.
Since the cell was closed and airtight, no loss of solvent by
evaporation was noticed. Four different electrolysis potentials,
EPR Studies of Lithium Phthalocyanine
namely, +0.1, +0.2, +0.4, and +0.7 V, were used to prepare
the LiPc. The electrolysis time was fixed as constant (1 h)
irrespective of the electrolysis potential since the time of
electrolysis may influence the size of the crystal and hence the
line width of the EPR spectrum.3g Since the resulting LiPc is
insoluble in acetonitrile, the electrolysis product was either
precipitated out at the bottom of the cell or sticking to the
electrode surface with poor adherence. It was observed that the
LiPc samples obtained in the presence of dissolved oxygen gave
complex EPR characteristics irrespective of the deposition
potential (data not shown). Thus, during electrolysis, the solution
was continuously purged with argon to remove dissolved oxygen
and constantly stirred using a magnetic stirring bar to facilitate
electrolysis and to avoid mass-transfer limitation. The constant
stirring also assisted to effectively remove the LiPc crystallites
from the electrode surface easily and exposed most of the
electrode surface during the entire period of electrolysis. The
i-t curves for this long-time bulk electrolysis were followed
and ensured that by the end of the electrolysis time the current
remains constant at the level of the background current. After
the electrolysis, even the small fraction of LiPc sticking to the
electrode surface was removed by shaking it in the solution after
additional solvent was added, and the solid microcrystalline
particles were filtered and dried at 90 °C under atmosphere to
obtain a shiny dark-green powder.
X-ray Diffraction and EPR Measurements. X-ray diffrac-
tion measurements were carried out with a Rgaku diffractometer
(model D/Max) for a wide angle typically for 2θ values from
4° to 50° using Cu KR radiation with λ ) 1.542 Å. The other
experimental conditions included 0.5° divergence and scatter
slits, 0.15 mm receiving slits, step scans with 0.04° steps and 6
s counting time at each step, and intensity measured in counts.
The X band, 9.77 GHz EPR measurements were carried out
using a Bruker ER 300 spectrometer with a TM110 microwave
cavity. Data acquisition and analysis were performed using an
IBM-compatible personal computer interfaced to the spectrom-
eter. Instrument control and data acquisition and processing were
performed using SPEX, a personal computer software developed
in our laboratory. L-band EPR measurements were carried out
using a custom-built reentrant loop-gap resonator. For EPR
measurements, the sample was prepared as follows. The
crystalline powder was encapsulated in a 2 cm long and 0.8
mm diameter gas-permeable Teflon tube (Zeus Industrial
Products, Columbia, SC), and the tube was sealed at both ends.
The sealed tube was inserted into a 3 mm diameter quartz EPR
tube capped at both ends. The EPR tube was carefully positioned
in the cavity with the sample at the center of the active volume.
The tube was continuously and gently flushed with purified gas/
gas mixtures. The first-derivative EPR spectra were integrated
and subjected to area and line-shape analysis. The effect of O2
on the EPR spectra of LiPc was studied by purging with a
mixture of purified O2 and N2 gases prepared in the desired
ratio using a precalibrated gas flow meter (Cole-Parmer, IL)
and subsequently passed through gas-impermeable silicone tubes
into the EPR tube containing the gas-permeable Teflon tube
embedded LiPc, made as described above.
EPR Absorption Line-Shape Analysis. The EPR absorption
line shapes were analyzed as pure Lorentzian lines using
commercial software PeakFit (SPSS, Inc., Chicago, IL). No
dispersion component of the resonance signal was necessary to
be included in the analysis, since in normal CW EPR spectros-
copy only the absorption component of the resonance signal is
observed, with the dispersion component being suppressed by
suitable phasing of the microwave bridge. In the fitting of the
J. Phys. Chem. B, Vol. 104, No. 17, 2000 4049
Figure 2. Cyclic voltammograms of 25 mM Li2Pc in dry acetonitrile
containing 0.1 M TBAP as supporting electrolyte: (A) Scan rate 0.1
mV s-1. The inset shows a magnified view of the first redox peaks (B)
Scan rate 0.01 mV s-1 in the potential range -0.4 V to +0.4 V covering
the first redox peaks alone. (C) Variation of peak currents with scan
rate (D) Variation of charge with deposition time for the first redox
peaks.
data, both the full width at half-maximum (fwhm) and the
amplitude were allowed to change for all the individual spectra
under the envelope. The best fit was assessed from the minimum
chi-square (χ2) and the maximum correlation coefficient (r2).
Results and Discussion
Electrochemical Oxidation of Li2Pc on the Pt Electrode
and Evidence for Nucleation of LiPc Deposition. Figure 2
shows the cyclic voltammogram of 25 mM Li2Pc (dilithium
phthalocyanine, Aldrich) at the potential sweep rate (V), 100
mV s-1, in dry acetonitrile. The entire CV pattern encompassing
the potential range from -0.5 to +0.9 V shows basically two
processes. The first process showing an oxidation peak at +0.06
V was quasi-reversible, as discussed later in detail, since a
cathodic peak is observed in equal magnitude as the counterpart
at -0.08 V in reverse sweep. The second process is an
irreversible oxidation, which occurs beyond 0.5 V (Figure 2A),
although there is no clear-cut peak shape. This peak is extended
over 0.3 V, and there is no cathodic counterpart. In a separate
experiment, the potential sweep in the anodic direction was
reverted at +0.4 V (Figure 2B; the sweep rate is 10 mV s-1),
encompassing only the first redox couple. It can be seen from
Figure 2B that the current steeply rises at the start of the anodic
peak, with the full width at half-maximum (obtained as 2(Ep -
EHM), where Ep is the peak potential and EHM is the potential at
half of the peak height) unusually narrow, about 38 mV. This
quantity is comparable neither with 90.6 mV reported for the
surface wave without any interaction among the adsorbate8 nor
with 28 mV reported for the solution-phase redox processes.9
Moreover, during the cathodic sweep, an overlap between the
forward and reverse sweeps (as seen in the Figure 2B) leading
to a “current loop” is noticed. In addition, a large potential
separation of cathodic and anodic peaks is also observed. The
overlap of the forward current-potential curve with the reverse
curve during potentiodynamic sweep resulting in the current
4050 J. Phys. Chem. B, Vol. 104, No. 17, 2000
TABLE 1: Cyclic Voltammetric Peak Parameters for 25 mM Li2Pc and 0.1 M TBAP in Acetonitrilea
anodic peak
V/mV s-1 Epa/V (Ag/AgCl) *Efwhm/mV ipa/µA
10 0.030 38.4 12.490
25 0.040 40.0 18.752
50 0.049 50.0 23.251
100 0.057 65.0 28.572
200 0.069 72.5 46.820
300 0.070 50.0 53.621
400 0.074 50.0 62.542
500 0.078 52.5 68.721
a
Efwhm ) 2(Ep - EHM), where Ep is the peak potential and EHM is the potential at half peak height. ipa and ipc are the anodic and cathodic peak
currents, respectively. Epa and Epc refer to the anodic and cathodic peak potentials.
loop has been shown theoretically to correspond to the
electrochemical reaction following the nucleation and growth
mechanism.10 However, such an observation of a current loop
is also possible in situations where the charge-transfer step is
followed by a coupled chemical reaction and the product of
the reaction has a lower oxidation potential than the starting
material.9 This might not be the case in the present study since
in such cases the redox peaks cannot be as sharp as observed
here and normally are broader, extending over 120 mV.9 Also
it is observed that the anodic to cathodic peak ratio (ipa/ipc, Table
1) is close to unity irrespective of the scan rate, suggesting the
absence of any coupled chemical reaction. The current loop,
sharp peak, and large potential separation observed in the present
work are characteristics of electrochemical phase formation
through the nucleation-growth mechanism.10,11 With this mech-
anism the formation of a critical nucleus on the substrate, which
requires high energy, is the slowest and rate-determining step,
and this is followed by almost explosive “growth” at large
overpotentials. The process at this peak is
charge transfer stacking
Pc2- y\z LiPc y\z (LiPc)crystal
After charge transfer, since the resulting neutral LiPc is not
soluble in acetonitrile, it is deposited on the surface and stacked
to result as crystallites. The observation of a current loop is
also an indication of the deposition of conducting LiPc
molecules. Due to the extended nature of this one-dimensional
solid, significant stabilization of the solid is realized through
intermolecular interactions. The adherence of this material on
the Pt surface was, however, found to be very poor.
The peak potentials, for both the anodic peak (Epa) and the
cathodic peak (Epc), were found to increase with sweep rate
(Table 1), a typical characteristic of the quasi-reversible redox
process. The magnitude of the potential shift, however, was
different for anodic and cathodic peaks. In the anodic step, the
slope of the Epa versus log(V) plot was 30 mV, which
corresponds to a calculated transfer coefficient, Rna, of 0.5. On
the other hand, the potential shift in the cathodic sweep was
much less, typically around 13 mV. This indicates that the
charge transfer in the cathodic stripping process is faster than
the anodic deposition.
The anodic peak current was found to vary linearly with V1/2
typical of diffusion-controlled deposition of LiPc. Table 1 also
includes the full width at half-maximum (Efwhm) of both the
anodic and cathodic peaks for various sweep rates. The Efwhm
of the anodic peak increases with an increase in sweep rate.
This can be interpreted in two ways. Since the charge-transfer
process is slightly sluggish unlike any normal nucleation process,
peak broadening is possible.9 On the other hand, sharper peaks
at low sweep rates may also be due to the fact that more time
is provided for the established nuclei to grow steadily, and the
Ilangovan et al.
cathodic peak
Qt/µC Epc/V (Ag/AgCl) *Efwhm/ mV ipc/µA Qt/µC
445.0 -0.065 80.0 -13.632 -62.8
228.00 -0.067 80.0 -19.460 -39.7
114.0 -0.074 90.0 -25.551 -32.3
71.2 -0.082 90.0 -35.412 -25.5
55.9 -0.082 95.0 -39.971 -15.8
37.0 -0.084 97.5 -50.394 -15.2
31.9 -0.085 97.5 -56.900 -13.0
28.1 -0.087 97.5 -60.682 -11.4
periphery of the growing nuclei expands two-dimensionally
along the surface, as well as growing into the solution three-
dimensionally, so that more LiPc is deposited, leading to the
steep rise in current. In other words, the diffusion layer thickness
is smaller in the low potential sweep rate ranges. The latter
explanation seems to be the most likely case for the following
reasons. This is consistent with the observation that at low sweep
rates the diffusion tail of the anodic peak does not decline as
steeply as in higher scan rates. Also the total charge (Qt) of
both anodic and cathodic peaks (Table 1) obtained from the
integration decreases with an increase in the potential sweep
rate, confirming that the amount deposited in the slow sweep
rates is quite high. The deposition and stripping phenomenon
is also evident from Figure 2D, where the total charge dispensed
during both deposition and stripping is proportional to time.
Another interesting aspect observed in the redox behavior of
LiPc is that the diffusion control of the reverse cathodic sweep,
where the peak current shows linear variation with V1/2. The
diffusion control of the anodic peak is understandable in that
the electroreactant, namely, Pc2-, is transported to the electrode
by diffusion through the diffusion layer in the bulk solution.
But the stripping process in any solid electrode is a surface
process, and hence the peak current is expected to increase
linearly with the scan rate.8 The present case, however, has
phenomenological similarity to the metal ion stripping from Hg
film electrodes.12 On Hg film, as soon as the reduction of metal
ions occurs, they are amalgamated and homogenized into the
bulk volume of the Hg film. Thus, in the stripping process, the
diffusion layer is set in the Hg, since the surface to volume
ratio is relatively higher.12 Since there is no such possibility
with the solid Pt electrode, it is more likely that the LiPc formed
on oxidation is not stuck on the surface unlike any metal ion
deposition; instead it either goes into the solution phase or is
adsorbed poorly on the surface, and growth occurs away from
the electrode surface. This apparently results in the solution-
phase redox-like characteristics. This hypothesis is further
supported by the observation that Qt of the forward anodic sweep
is higher than Qt of the reverse cathodic sweep (Table 1). It
ultimately shows that not all the deposition formed on the
forward step is reduced back to LiPc-, as it should be in the
case of the surface redox process.8 Thus, LiPc deposition appears
more like a conducting polymer phase formation, where the
monomeric compound is oxidized, and the oxidized species goes
back into solution to chemically react with similarly generated
species, and the polymer chain grows.13 Once the concentration
of the oligomer near the electrode exceeds the solubility, it is
then adsorbed onto the surface.
Electrocrystallization and Growth Mechanism of LiPc. In
any case of preparation of a desired material through electro-
deposition, one has to establish the mechanism of growth, since
the very nature of growth can affect both the size and properties
EPR Studies of Lithium Phthalocyanine J. Phys. Chem. B, Vol. 104, No. 17, 2000 4051

Figure 3. Chronoamperograms of 25 mM Li2Pc in dry acetonitrile containing 0.1 M TBAP as supporting electrolyte. (A) Set of i-t curves at
various stepping potentials as indicated in the figure. The inset shows a magnified view of t0 and region I. (B) Variation of i - i0 with (t - t0)1/2
corresponding to the rising portion (region II) of i-t curves. (C) Nondimensional plots of (i/im)2 versus t/tm. The two extreme cases (lines a and b)
of progressive and instantaneous nucleation mechanisms were simulated using the equation (i/im)2 ) [1.2254/(t/tm)]{1 - exp[-2.3367(t/tm)2]}2 and
(i/im)2 ) [1.9542(t/tm)]{1 - exp[-1.2564(t/tm)]}, respectively [ref 17b,c]. The points shown in the figure correspond to the experimental values at
stepping potential 0.085 V. (D) Cottrell plot obtained at different stepping potentials as indicated in the figure.

of the resulting crystals.5 Despite the fact that there has been a
great interest shown in such an evaluation of the deposition and
growth mechanism of metals, few insights have been gained in
the case of organics or organometallics. This is because the issue
in question, namely, the formation of a “critical nucleus or
ad atom” after the charge-transfer step, is different in the case
of deposition of organics. In the case of metal ion deposition,
the metal atom simply sticks to the surface as an adatom and
forms the critical nucleus. But in the case of organics, the
deposits are formed on the surface after charge transfer followed
by some chemical steps. These coupled chemical steps in many
organic depositions make the processes very complicated. The
best example is the case of conducting polymers such as
polyaniline and polypyrrole, where the chain growth reaction
of the polymer is interposed between charge-transfer and
deposition steps as discussed above.13 In the case of electro-
crystallization of low-dimensional solids such as LiPc, the
solubility product of the depositing material dictates the
conditions required for critical nucleus formation. Surface
deposition occurs when the concentration near the electrode
surface exceeds the solubility product.5 The potential step
chronoamperometric technique, where the change in the current
is followed with time after stepping the potential to a desired
value, has been established as a superior method for studying
phase formation kinetics and the growth mechanism. The
advantage of this method in studying phase formation and crystal
growth is that the electrode can act as an initiator and facilitate
deposition of the substrate.13c This approach has been very
successfully used in metal deposition for which various theories
and models have been extensively worked out.14
A series of potentiostatic i-t transients were recorded in the
0-10 s window for different stepping potentials (Es), as
illustrated in Figure 3A. These experiments were carried out
by stepping the potential of the working electrode from an initial
value, -0.2 V, where there is no faradaic process, to a set final
potential, Es. In accordance with the CV results above, chrono-
amperograms at different potentials showed the characteristics
of the phase formation process following the nucleation step.14
The i-t curves in Figure 3A have three different regions,
namely, I-III. When the working electrode potential is stepped
up, the current increases instantly due to double-layer charging,
and with time it monotonically comes down to the background
current (region I; see the inset in Figure 3A) in general for solid
electrodes, in less than 1 s.9 If the electroactive species is present
4052 J. Phys. Chem. B, Vol. 104, No. 17, 2000 Ilangovan et al.

in solution, then the oxidation/reduction of this species over- TABLE 2: Chronoamperometric Analysis of Nucleation and
takes. In such a case, instead of the current coming down to Growth of LiPc on a Pt Electrodea
the baseline in milliseconds, a smooth exponential decrease in Es/V to/s (tm - t0)/s 106 (im - i0)/A cm-2 10-7N/cm-2
current is noticed due to the charge-transfer process over time, 0.065 0.020 1.560 6.4957 1.3963
and the course of the decreasing pattern of the i-t curve depends 0.075 0.020 1.150 20.1000 1.8941
on the mechanism of charge transfer.15 As a matter of fact in 0.085 0.020 0.590 30.8428 3.6919
the present case (Figure 3A), an increase in current in region II 0.100 0.020 0.275 59.5714 7.9209
is observed after double-layer charging. That is, the i-t 0.125 0.020 0.105 110.5713 20.7457
0.150 0.015 0.050 234.8571 43.5649
transients result in well-defined peaks. This rise in current is 0.175 0.015 0.029 306.8453 75.1118
due to an increase of the electroactive area due to the formation 0.200 0.010 0.015 438.8345 145.2162
of conductive deposits, and this new heterogeneous phase a
The number density for higher stepping potentials beyond +0.2 V
behaves as an extension of the electrode surface. In the present
could not be obtained since the tm was very less, overlapping with t0.
case, the extended electrode surface grows three-dimensionally
into the solution, and further oxidation of Pc2- to LiPc occurs
on the crystal face normal to the stacking axis because of the or depletion zones (area under which a concentration gradient
high degree of conductivity anisotropy in one-dimensional sets up due to electrochemical reaction) about each nuclei
conductors (σ|/σ⊥ = 103). This results in the observation of develop since the growth is controlled by spherical diffusion
crystalline needlelike structures of LiPc, as later confirmed by (where the flux depends on the radius of the diffusion zone) of
micrographs. After the current rises to a maximum, it starts once Pc2-. Inside each of the diffusion zones about a nucleus, the
again to decrease in region III. It can also be seen that the concentration of Pc2- decreases exponentially with distance
decreasing portion of the i-t curve in region III is merged into toward the nucleus.9 These diffusion zones around growing
a common line at higher Es, typically at +0.1 and +0.125 V in nuclei advance readily and much more rapidly than the
Figure 3A. perimeters of the nuclei themselves, and at the focus of the
The principal nature of the i-t curve is the rising portion diffusion zone the nuclei act as a point sink.17b Since the
(region II) corresponding to the growth of the electroactive area, diffusion zones of nuclei grow much faster than the nuclei
as established nuclei grow and new nuclei are formed. The peripheries themselves, they overlap soon with neighboring
nature of this rising portion reflects the mechanism of growth. diffusion zones, leading to the current as observed in Figure
The relation of i with respect to t in this time domain is different 3A. Once the overlap occurs, the diffusion is no longer spherical
for different mechanisms of growth.16 By establishing the power- and transforms to linear diffusion (where the flux is independent
law relationship of the current and time corresponding to the of the radius of the diffusion zone). This problem of overlap of
rising portion, the respective mechanism is predicted. Various diffusion zones has been treated by different groups, and various
relationships have been derived between the variants time (t - conflicting formulations have been presented.17 In all these cases,
t0, where t0 is the time at which the rising portion starts; see the major difference of opinion is in quantifying the extended
the Figure 3A inset) and current in this region for various electrode surface area in the case of progressive nucleation.
deposition mechanisms. The variation of current in this region However, all these models agree that in the case of instantaneous
of the present study is found to be linear with (t - t0)1/2 (Figure nucleation the original theory proposed by Scharifker et al.17a,b
3B), indicative of instantaneous nucleation and mass-transfer- is appropriate as recently proved.17f Further validation of
controlled growth of hemispherical nuclei as required by the instantaneous nucleation is also obtained from commonly used
equation,17 “nondimensional” plots suggested by Scharifker, as illustrated
in Figure 3C. The experimental data obtained match the
i - i0 ) nFπN(2Dc)3/2M1/2(t - t0)1/2/F1/2 (1) instantaneous nucleation model. However, deviations are seen
in Figure 3C in region III. This is presumably due to the fact
where nF is the molar charge of the depositing species, D is its
that this model assumes overlap of hemispherical diffusion zones
diffusion coefficient, c is its concentration (mol‚cm-3), M is
although in the present case they are not perfect hemispherical
molecular weight, and F is the density. Diffusion control is also
diffusion zones as described below.
evidenced from the fact that the i-t curve in region III merges
The nucleation parameters are estimated as follows. The time
into a common line at higher stepping potentials. The instan-
to reach the maximum (tm) and the current at the maximum
taneous nucleation model represents a situation in which all
(im) are dependent on the Es (Table 2). When the Es becomes
nucleation sites are activated at the beginning, t0. The charac-
more positive (or the applied overpotential, Es- E0 gets larger),
teristic parameter N in the above equation defines the number
the number density increases, and this shortens the time required
of nuclei on the surface known as the “number density”, and it
for the overlap of the diffusion zones. As a result, the observed
depends on the stepping potential (Es), but for a given Es it
im increases while tm decreases, as the stepping potential
virtually remains constant throughout the time of the experiment
becomes more positive. N is obtained from tm as follows:
until the peripheries of the nuclei overlap, which is highly
improbable as described below, according to this mechanism.17
N ) 1.2564/tmπkD (2)
The above equation is applicable to a single growing nucleus
without any other influences such as overlap of similar nuclei
and thus considered as an ultramicroelectrode. However, in where the constant k is defined as k ) 4/3(8πcM/F)1/2. Table 2
practice on any conventional electrode getting an isolated summarizes the calculated N values for various stepping
nucleus is impossible since the area of any conventional potentials. The D value required in the estimation of N was
electrode is relatively large, a huge number of similar nuclei obtained from the current transients at long times of Es of +0.15
appear simultaneously, and their direct or indirect influence on and +0.175 V (Figure 3D), as the current decay is described
each other is inevitable. Once the nuclei are formed on the by the Cottrell equation
surface, all of them grow with the same rate throughout the
experiment time. As time progresses, the hemispherical diffusion i ) (nFAcD1/2)/(π1/2τ1/2) (3)
EPR Studies of Lithium Phthalocyanine
Figure 4. Micrographs of LiPc obtained at various deposition potentials, magnification 400, electrolysis time 1 h.
where A is the area of the electrode. The average D value was
2.40 × 10-8 cm2 s-1. This value of the diffusion coefficient is
smaller but not uncommon as many of the macrocyclic redox
proteins have a similar range of D values.17h The N values in
Table 2 are on the order of 105-107 cm-2 as in the case of
many depositions undergoing this mechanism in aqueous and
molten salts.18 The above results show an important conclusion
that the LiPc deposition mechanism does not change with Es,
as reported in some cases that it switches over from progressive
to instantaneous nucleation.17c,e
XRD and EPR Analysis of Electrodeposited LiPc. After
the redox behavior and electrochemical phase formation mech-
anism were understood, the LiPc was electrocrystallized at four
different electrolysis potentials, namely, +0.1, +0.2, +0.4, and
+0.7 V, covering a wide potential range. All four deposition
potentials resulted in green-black microcrystalline powders.
Microscopic examination of the powders obtained at +0.4 and
+0.7 V (Figure 4) showed that needle-shaped crystals were
obtained, confirming one-dimensional growth5 of LiPc. Since
constant stirring was applied during the electrocrystalization,
needles of various sizes are observed in Figure 4. The maximum
size of crystals obtained from micrographs was about 80 µm.
The needles were very fragile. On the other hand, in the lower
deposition potentials, namely, +0.1 and +0.2 V, a considerable
amount of the amorphous form was obtained.
J. Phys. Chem. B, Vol. 104, No. 17, 2000 4053
EPR measurements were performed at the X-band to inves-
tigate the paramagnetic properties of these materials. Figure 5
illustrates the X-band EPR spectra obtained under N2 atmosphere
for all four samples prepared at four different deposition
potentials. The EPR spectra showed two symmetric components,
designated here as A and B, with two different line widths for
the samples crystallized at +0.1 and +0.2 V. But in cases of
samples obtained at 0.4 and 0.7 V, only one prominent peak,
A, was observed. In general, the EPR spectra of the powder
samples did not show any significant anisotropy with respect
to magnetic field orientation, although all three known crystal-
line forms show such orientation effects in single crystals.3 Since
the total spectrum in any of these cases is symmetrical, showing
that the species have slightly different g values and are π
radicals, the only factor that differs among these lines is the
relaxation time (line width), and this allows one to observe both
lines separately. Moreover, as seen in Figure 5, the deposition
potential has significant influence on the magnitudes of these
peaks. The line, with very sharp line width (about 5 mG), is
maximum in the samples obtained at electrolysis potentials +0.4
and +0.7 V. The anoxic line width of 5 mG obtained in the
present work is smaller than the value 26 mG reported for the
x form in the literature.3g The higher value reported previously
might be due either to instrumental broadening or the small
deformation of the x form. On the other hand, the powders
4054 J. Phys. Chem. B, Vol. 104, No. 17, 2000 Ilangovan et al.

Figure 5. X-band EPR spectra of LiPc under nitrogen for samples obtained using various deposition potentials. Spectral acquisition parameters
were modulation frequency 12.5 kHz, modulation amplitude 25 mG, microwave power 0.79 mW, time constant 2.5 ms, number of scans 3, and
scan time 5 s.

Figure 6. Powder XRD patterns of LiPc obtained at various deposition potentials. Cu KR radiation with λ ) 1.542 Å was used. The other
experimental conditions were scan width 0.04° and counting time 6 s. The peaks are indexed on the basis of refs 3f,g and 19c.
obtained at electrolysis potentials +0.1 and +0.2 V have the
maximum proportion of the component with large line width.
It is not clear whether the two components observed are due to
two different crystalline forms or due to two magnetically
different species of a single crystalline phase. Thus, the samples
were subjected to XRD analysis to evaluate the crystalline
nature.
The XRD patterns of the samples obtained are shown in
Figure 6. The diffraction peaks were analyzed on the basis of
the information available in the literature.3f,4a,19 In general,
almost all major reflections are well-resolved, indicating that
the resultant powder in all four experiments are with a high
degree of uniaxial ordering of the microcrystalline domains.
However, comparison of the magnitude of peaks shows that
the intensity is 3 times higher for the samples deposited at +0.4
and +0.7 V than the samples deposited at +0.1 and +0.2 V.
This is consistent with the micrographs presented in Figure 4.
In all four samples one can consistently notice the occurrence
of one prominent diffraction peak, at a 2θ value of 6.28°
corresponding to the (100) plane reflection of the x form.3f Also
it is seen that the magnitude of this is comparable for the samples
+0.1 and +0.2 V as well as +0.4 and +0.7 V. Although the
formation of the R form is common for phthalocyanines3f in
chemical vapor deposition at room temperature, in the case of
LiPc it has been found that the preferential formation of the x
form is due to the lower oxidation degree of lithium (+1) as
compared to the metal phthalocyanines such as CuPc or NiPc.
As a consequence the net negative charge on the phthalocyanine
macrocyclic ring is reduced so that the magnitude of the
interaction among the macrocycles in the stack as well as in
the nearby stacks is affected. However, it is important to notice
that the powder patterns obtained for samples of different
deposition potentials showed significant variations.
Apart from the (100) plane reflection (intensity scaled to
100%), other major reflections corresponding to (200), (300),
(221), and (002) planes were also observed as described in
Figure 6. On the other hand, samples electrodeposited at +0.1
and +0.2 V showed additional diffraction peaks, which cannot
be attributed to any diffraction of the x form (Figure 6). This is
contrary to the previous report that electrochemical oxidation
of Li2Pc exclusively yields the x form of LiPc films in
acetonitrile.3g The potentiostatic deposition used in the present
case clearly demonstrates that the LiPc phase formation depends
on the electrodeposition potential. This observation is very
critical since only the x form is active for Heisenberg spin
exchange as described in the Introduction, and useful in EPR
EPR Studies of Lithium Phthalocyanine
Figure 7. EPR line-shape analysis of the LiPc obtained at various deposition potentials. The theoretical line calculated from the optimized parameters,
fwhm and intensity, is shown as the solid line, while the points represent the experimental values, acquired at anaerobic conditions. The fitting
program used the Levenberg-Marquardt optimization algorithm. The r2 values were better than 0.99 in all the cases.
oximetry. A careful examination of the XRD pattern (Figure
6) shows that the patterns are very similar for materials obtained
at +0.4 and +0.7 V, which are far more positive than the formal
redox potential (E0) +0.05 V. Also the XRD patterns are
comparable for the samples obtained at +0.1 and +0.2 V, which
are close to the E0. There are two possible ways to interpret the
additional XRD peaks obtained for the latter cases. The first
explanation is to consider this powder to be a mixture of two
phases, among which one is the x form. The second possibility
is to consider the deformation of the tetragonal unit cell of the
x form as suggested by Brinkman et al.3f But the second
possibility is highly improbable since it cannot explain the high-
intensity peak at a 2θ value of 9.22°. Moreover, the preparations
were carried out in the same solvent (acetonitrile), and hence,
the deformation of the tetragonal unit cell due to occlusion of
solvent molecules cannot be a valid explanation. Thus, the
additional peaks must be due to the presence of an additional
phase. These additional peaks are analyzed on the basis of a
report by Homborg et al.19c Actually these peaks do not
correspond to the R form since the 100% peak is not observed
at 2θ equal to 6.78°.3f Instead, it is observed at 9.22°, indicating
the presence of the β form.19c The other major peaks of lower
angle diffraction at 2θ values of 6.950° for (001), 14.07° for
(002), and 18.65° for (101) are observed in accordance with
the β crystal structure. The obtained intensities differed by less
than 3%, especially in the lower diffraction angle, and this might
be due to the absorption of X-ray at these angles as reported
previously.3f These results conclusively prove that the samples
obtained at +0.4 and +0.7 V are primarily the x form, while
the other two obtained at +0.1 and +0.2 V are mixtures of β
and x forms. The composition of the mixture is almost the same
for samples obtained at both +0.1 and +0.2 V. Thus, the two
lines observed in the EPR spectra for the +0.1 and +0.2 V
samples are due to two different phases. Correspondingly, the
only one extremely sharp EPR line observed for +0.4 and +0.7
V samples corresponds to the x form, and the additional broad
line observed for +0.1 and +0.2 V may correspond either to
J. Phys. Chem. B, Vol. 104, No. 17, 2000 4055
the β form or to the amorphous form. However, a small amount
of the amorphous form of LiPc was present even in the samples
obtained at +0.4 and +0.7 V, which is not reflected in XRD
but seen in Figure 7 (see later). From the results of electro-
crystallization studies of the present work, it is clear that the
basic deposition mechanism is the same in all four potentials,
while only the rate of deposition of LiPc is different at different
potentials as reflected in the resulting number density. It seems
the slow deposition of LiPc at lower deposition potentials such
as +0.1 and +0.2 V, where the nucleation number density is
low, leads to a mixture of x and β forms and also largely to the
amorphous form. However, at higher potentials where the
number density is higher, the x form is preferably formed.
Quantitative analysis of these two phases was performed
through EPR peak fitting analysis. The first-derivative EPR
spectra were integrated to absorption shape, and the absorption
peaks were analyzed. We performed the analysis on absorption
profiles and obtained quantitative information regarding the
composition of different species. Initial fitting analysis showed
that the lines were very close to Lorentzian shape and could be
fit to the function20
Y ) Ymax[Γ 2/Γ2 + (B - Br)2] (4)
where B is the magnetic field and Br is the resonance field. Γ
is the half-width at half-maximum. Figure 7 illustrates the curve
fitting of the experimental EPR data with the two-peak model
for different samples. It is seen from Figure 7 that the theoretical
line shape calculated from the fit matches very well with
experimental data, indicating that the Lorentzian model of shape
describes the absorption profile appropriately. The line-shape
analyses of the samples prepared at the different deposition
potentials showed evidence for two components (A and B) with
slightly different g factors. The relative intensities of these two
components obtained from the double integration of the spectra
depended on the deposition potential. For example, for samples
prepared at +0.1 and +0.2 V, the broad line with a peak-to-
4056 J. Phys. Chem. B, Vol. 104, No. 17, 2000
Figure 8. Effect of microwave power on the intensity and width
(fwhm) of the two deconvoluted EPR absorption peaks, peak A and
peak B, for samples obtained at +0.4 and +0.2 V, respectively.
peak separation of 0.65 G is maximum with more than 90% of
the intensity. On the other hand, the samples prepared at
deposition potentials +0.4 and +0.7 V showed the higher ratio
of the narrow line width component to the broad peak
component. This is consistent with the XRD pattern that the
samples prepared at +0.7 and +0.4 V had almost only the x
form while the other two samples contained a mixture of both
x and β forms.
Further experiments on saturation properties of the decon-
voluted lines were performed. Such an experiment is very useful
to define the right microwave power, to employ in oximetry
experiments. Figure 8 illustrates the effect of the microwave
power on the peak parameters, namely, the peak width and the
intensity, for the samples obtained at +0.2 and +0.4 V. Similar
trends were obtained for the other three samples. The peak
parameters were obtained by EPR line-shape analysis. The full
width at half-maximum (fwhm ) 2Γ) shown in the figures is
related to the peak to peak width (∆Bpp) in the first-derivative
EPR spectrum as follows:20
∆Bpp ) (2/x3)Γ (5)
The intensity of the peak is obtained from the integrated area
under the peak. It can be seen that the line width of the narrow
peak corresponding to the x form remains constant in the lower
power region and starts increasing beyond 50 µW. Also the
intensity of this peak increases linearly with (power)1/2. How-
ever, at high power the intensity of the absorption curve no
longer maintains linearity. It is clear from Figure 8 that the
saturation of the x form occurs above 50 µW and for the β
form understandably linearity is maintained even at higher
power.
Ilangovan et al.
Figure 9. Effect of room air and nitrogen on the EPR spectrum of
LiPc obtained using a deposition potential of +0.4 V. Spectral
acquisition parameters were modulation frequency 12.5 kHz, modulation
amplitude 2 mG, microwave power 2 µW, time constant 2.5 ms, number
of scans 1, and scan time 5 s. The spectrum in room air was obtained
with modulation amplitude and 200 mG and microwave power 25 µW.
EPR Oximetry Using LiPc. The four samples were tested
for oxygen-induced line-broadening to evaluate their usefulness
for EPR oximetry applications. The role of molecular oxygen
on the EPR line width in thin films of x LiPc is well established.3
As a first step toward evaluating these samples for oximetry
applications, the rapidity of oxygen diffusion (response time)
for samples prepared at various deposition potentials was
evaluated using the change in EPR line width with time in
samples exposed to room air. The samples encapsulated in a
gas-permeable Teflon tube inside a 3 mm quartz tube and kept
under nitrogen at atmospheric pressure showed very sharp EPR
lines. When the flow of nitrogen was stopped, allowing the room
air to counterflow into the tube, broadening of the EPR signal
was observed, due to diffusion of molecular oxygen inside the
microchannels, replacing the nitrogen in thermodynamic equi-
librium inside. Since the molecular dimensions of both oxygen
(O2) and nitrogen (N2) are 2.8 × 3.9 and 3.0 × 4.1 Å2,
respectively,21 they easily go through the microchannels of the
x form LiPc with diameter inside the quadratic lattice about
6.0 Å as illustrated in Figure 1. A typical X-band EPR spectrum
of the x form of LiPc at very low modulation (2 mG) and power
(2 µW), under anoxic conditions, showed a peak to peak line
width of 5 mG (Figure 9). When the sample was exposed to
room air, the peak broadened and the amplitude decreased in a
few seconds and a weak broad signal was observed. This
indicates that the spin-spin relaxation time, T2, between O2
and the excited state of LiPc is shortened drastically. However,
when the sample was subsequently resaturated with pure
EPR Studies of Lithium Phthalocyanine J. Phys. Chem. B, Vol. 104, No. 17, 2000 4057

TABLE 3: Reduced Diffusion Coefficient, Dred, Obtained

from the Diffusion Kineticsa
Ed/V (Ag/AgCl) Dred/s-1 Ed/V (Ag/AgCl) Dred/s-1
+0.1 6.73 × 10-4 +0.4 9.57 × 10-4
+0.2 7.95 × 10-4 +0.7 4.75 × 10-4
red ) Dl , where D is the absolute diffusion coefficient and l is
aD 2

the length of the diffusion channel.

molecules. When exposed to O2, a fraction (c) of mobile spins

are converted as “fixed” spin states by coupling with O2.3k Thus,
the observed total Γ is represented by

ΓT ) (1 - c)Γ0 + cΓ1 (7)

where Γ0 and Γ1 are the widths corresponding to c ) 0 and c
) 1. Since Γ0 , Γ1

Figure 10. Diffusion kinetics of molecular oxygen into the micro- ct ) (ΓTt - Γ0)/Γ1 (8)
channels of the x polymorph of LiPc, followed by means of the change
in line width as a function of time for various samples. Also assuming that this is true at any p(O2)

nitrogen, the signal sharpened again and the amplitude fully Mt/M∞ ) ct/c∞ ) (ΓTt - Γ0)/(ΓT∞ - Γ0) (9)
returned (Figure 9). This was reproducible for more than 10
times of nitrogen-air cycling, suggesting that the process is Then eq 6 can be written as3k
reversible and there is no permanent change to the LiPc crystals
due to oxygen. Figure 10 illustrates the oxygen responsivity of (ΓTt - Γ0)/(ΓT∞ - Γ0) )
∑[1/(2m + 1)2] exp{-D(2m + 1)2π2t/l2}
the samples measured as the change of line width with time. In
all cases the EPR line corresponding to the x form was followed, 1 - (8/π2) (10)
although the fractions were smaller in the cases of the samples
The experimental data shown in Figure 10 showed significant
obtained at +0.1 and 0.2 V.
deviations when we tried fit them to the above equation,
The EPR line-broadening in the solid state occurs due to the
especially in the lower time domains. This is understandable,
diffusion of O2 into the microchannels and subsequent spin-
since the samples have been encapsulated into gas-permeable
spin interaction through the Heisenberg exchange mechanism.22
Teflon tubes so that the diffusion characteristics of the Teflon
Thus, the diffusion characteristics of these materials will be of
tube may influence the curve. However, for the purpose of
fundamental interest in evaluating their efficiency for oximetry
comparative evaluations, the above equation was used to obtain
applications. All four samples were evaluated for oxygen
the reduced diffusion coefficient, Dred ) D/l2, to get an idea of
responsivity. In all the cases, the sample was first flushed with
which of the four samples is the most suitable for oximetry
N2 and the flow was stopped, allowing the room air (ap-
applications. Dred is estimated analytically as follows. The value
proximately 150 mmHg of pO2) to counterflow into the EPR
of t/l2 for which Mt/M∝ ) 0.5 is defined as follows, with the
tube, and the change in line width was followed with time
approximate error being 0.001%:
(Figure 10).
First, it is assumed that the particle sizes are random and are
D ) 0.049/(t/l2)0.5 (11)
in the same order since the electrocrystallization was fixed to
constant time in all four cases, as it is known that the size
The computed Dred values have been summarized in Table 3. It
critically depends on the time of electrolysis. Second, the
should be noted that the Dred values are not the absolute diffusion
diffusion is assumed to be concentration-independent Fickian-
coefficients of the O2 into the crystals; it is also influenced by
type diffusion23 so that the diffusion coefficient D of O2 is
the Teflon surrounded by them. However, the influence is
expected to be constant at any given concentration. Third, it is
common in all the cases. It can be seen from these values that
also assumed that the microcrystals do not swell upon sorption
the samples obtained at deposition potential +0.4 V show a
of O2; i.e., at any time during the sorption the thermodynamic
maximum value, indicating that the sample obtained at 0.4 V
volume is maintained constant. On the basis of these assump-
is the optimum for oximetry application. It is important to note
tions, an appropriate solution of the diffusion equation may be
here that while the other characterizations do not show any
written as23
discernible difference between +0.4 and +0.7 V samples, the
diffusion coefficient evaluation proves that the former is
Mt/M∝ )
superior.
1 - (8/π2) ∑[1/(2m + 1)2] exp{-D(2m + 1)2π2t/l2} (6) As the next step for quantitative use of LiPc in oximetry
measurements, a calibration curve was constructed using the
Here Mt is the total amount of O2 adsorbed by the crystals at change in the line width with partial pressure of oxygen pO2.
time t and M∝ is the equilibrium sorption attained after infinite Since the real application will be in tissues with a large aqueous
time. l is the length to which diffusion occurs. It should be environment, a calibration curve was obtained in aqueous
remembered that the amount of O2 sorbed in EPR oximetry is solution using L-band EPR instrumentation. The LiPc was taken
obtained indirectly from the broadening of the line width. From in a gas-permeable tube containing saline solution. The sample
the studies of Bensebaa and Andre3k the Mt can be correlated was first purged with nitrogen gas, and then the desired pO2
to Γt. In the absence of O2 the spin states exist in the “mobile” gas mixture was allowed to saturate. All the measurements were
state since there is strong exchange between the stacked made after a constant peak amplitude was reached, typically
4058 J. Phys. Chem. B, Vol. 104, No. 17, 2000
Figure 11. Effect of the partial pressure of oxygen pO2 on the EPR
spectrum of LiPc electrodeposited at +0.4 V: (a) 0 mmHg, (b) 20
mmHg, (c) 120 mmHg. The inset is a calibration graph in the form of
line width versus pO2.
after about 10 min. A linear calibration curve, with the
correlation coefficient 0.98 in the 95% confidence level, was
obtained (Figure 11) for up to 100 mmHg pO2. The sensitivity
estimated from the slope (9.56 mmHg/pO2) is approximately
1.5 times higher than that reported for the LiPc single-crystal
oximetry experiments.1b This may be due to the fact that in the
microcrystalline powder the surface area is very high and the
molecular oxygen has to penetrate only on the micrometer scale
to effectively exchange the spin state. These results indicate
that this method using the material obtained in the present work
can be applied to evaluate pO2 in any in vivo application in the
partial pressure up to 100 mmHg, the case in many of the
phathophysiological conditions. Further work on the measure-
ments of in vivo oximetry in biological systems is in progress.
Summary and Conclusions
The present work indicates that the deposition potential plays
an important role in the preparation of desired forms of LiPc
crystals. Electrodeposition is found to follow the electrochemical
phase formation route as in the case of any metal deposition.
The detailed insights into the deposition mechanism indicate
that the nucleation pathway is instantaneous and the three-
dimensional growth is controlled by the diffusion of the reactant
through the bulk solution. While lower deposition potentials,
which are very close to the E0 of the redox process, yield a
mixture of x and β phases, the deposition potentials very far
from the E0 yield almost exclusively the oxygen-sensitive x
form. Consistently, the EPR studies show a single component
with a sharp line for the x form. Two lines, a broad line with
a line width of about 650 mG and another very sharp line with
a line width of about 5 mG, corresponding to the x form and
the β or amorphous form are observed for the former case.
Quantitative EPR analysis also confirms that the ratio depends
on the deposition potential. Needle-shaped microcrystals are
formed at deposition potentials +0.4 and +0.7 V, and mostly
amorphous powder was obtained at lower deposition potentials,
+0.1 and +0.2 V. The EPR line shape of the crystals obtained
Ilangovan et al.
at +0.4 V is very sensitive to molecular oxygen and hence is
ideal for EPR oximetry. Oximetry experiments reveal that the
x form of LiPc obtained by the present method is highly suitable
for oxygen measurements in aqueous media. Further studies of
the stability of LiPc in biological tissues with development of
appropriate pretreatments to maximize biocompatibility will be
needed to realize the full potential of this material as a biological
oximetry probe.
Acknowledgment. We thank Dr. A. Manivannan, Depart-
ment of Physics, University of West Virginia, for his help in
acquiring the XRD data and valuable discussion. This work was
supported by National Cancer Institute Grant CA-78886 and
NIH Grants GM-58582 and RR-12190. P.K. was also supported
by an Established Investigator Award from the American Heart
Association during the tenure of this study.
References and Notes
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C.; Dunn, J. F.; Swartz, H. M. Brain Res. 1995, 685, 91. (b)Liu, K. J.;
Gast, P.; Moussavi, M.; Norby, S. W.; Vahidi, N.; Walczak, T.; Wu, M.;
Swartz, H. M. Proc. Natl. Acad. Sci. U.S.A. 1993, 90, 5438. (c) Smirnov,
A. I.; Norby, S. W.; Walczak, T.; Liu, K. J.; Swartz, H. M. J. Magn. Reson.
B 1994, 103, 95. (d) Dunn, J. F.; Ding, S.; O’Hara, J. A.; Liu, K. J., Rhodes,
E.; Weaver, J. B.; Swartz, H. M. Magn. Reson. Med. 1995, 34, 515.
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