Journal of Photochemistry

and Photobiology,

A: Chemistry,

48 (1989)

291

- 301

291

PHOTOPHYSICS
AND PHOTOCHEMISTRY
OF
PHENOSAFRANIN
DYE IN AQUEOUS
AND
ACETONITRILE
SOLUTIONS
K. R. GOPIDAS

and PRASHANT

Notre Dame Radiation

(Received

November

Laboratory,

8, 1988;

V. KAMATT
Notre

Dame,

IN 46556

in revised form February

(U.S.A.)

10, 1989)

Summary
The singlet and triplet excited state properties of phenosafranin dye
were characterized in aqueous and acetonitrile solutions. The singlet excited
state exhibited an absorption maximum at - 430 nm and a lifetime of 930 ps
in aqueous medium. The transient absorption spectra of the protonated and
unprotonated forms of excited triplet were investigated by the laser flash
photolysis technique. The protonated phenosafranin triplet had absorption
maxima at 380 nm (E = 11000 M-i cm-l), 615 nm (E = 9700 M-l cm-) and
665 nm (E = IO 800 M-i cm-) and the unprotonated phenosafranin triplet
had absorption maxima at 410 nm (E = 8800 M-l cm-), 700 nm (e = 6900
M-r cm-) and 790 nm (E = 11600 M- cm-) in aqueous medium. The pKa
of the protonated triplet phenosafranin was found to be 7.25. Diffusioncontrolled quenching of the excited phenosafranin triplet by amines led to
the reduction of the dye. The absorption spectra of the semireduced phenosafranin, which was characterized in acetonitrile, exhibited absorption
maxima at 440 nm (e = 29 000 M- cm-) and 870 nm (E = 19000 M-
cm-).

1. Introduction
Phenosafranin, 3,7_diamino-5phenylphenazinium chloride (PHNS+), is
an azine dye that absorbs strongly in the visible. Reversible electrochemical
reduction and long-lived excited states make dyes such as PHNS+ potentially
useful as photosensitizers in energy and electron transfer reactions. Such
dyes have important applications in extending the absorptive range of large
bandgap semiconductors and improving the performance of photoelectrochemical devices. With the aid of a diffuse reflectance laser flash photolysis
technique we have recently shown that PHNS+ can efficiently inject an

TAuthor

to whom

lOlO-6030/89/$3.50

correspondence

should be addressed.
0 Elsevier Sequoia/Printed

in The Netherlands

292

Phenosafranin

electron from its excited singlet state into the conduction band of the TiOz
semiconductor [ 11. Applications of PHNS+ in other photoelectrochemical
devices have also been reported recently [ 2 - 41.
An attempt has been made previously to characterize long-lived
transients generated upon excitation of PHNS+ in aqueous solutions [ 41. But
the potential usefulness of dyes such as PHNS+ makes it necessary to investigate their photophysical and photochemical properties in greater detail. We
have now carried out a detailed spectral and kinetic study of singlet and
triplet excited states of PHNS+ in aqueous and non-aqueous media with the
aid of time-resolved picosecond and nanosecond laser flash photolysis.

2. Experimental details
2.1. Materials
PHNS+ (Sigma) was purified chromatographically over silica gel (Sigma,
chromatography grade, 100 - 200 mesh) with benzene-methanol (4: 1)
mixed solvent as eluent. It should be noted that the commercially supplied
PHNS+ dye contained considerable amounts of impurities that could not be
excluded by the usual precipitation or crystallization techniques. If not
removed, these impurities can affect the absorption and emission properties.
Purification by column chromatography gave satisfactory results. All other
chemicals and solvents were commercial products of reagent grade or better
and were used as supplied.
2.2. Methods
All experiments were performed at ambient temperature (300 + 1 K)
unless otherwise stated, and solutions were deaerated by bubbling with
nitrogen or argon. Absorption spectra were measured with a Perkin-Elmer
3840 diode array spectrophotometer. Corrected fluorescence emission
spectra were recorded with an SLM photon-counting spectrofluorometer.
Fluorescence quantum yields were measured by the optically dilute relative
method [6] with a solution of rhodamine 6G in air-saturatedethanol as the
standard (#f = 0.95 [6,7]).
2.3. Optical measurements
Fluorescence lifetime measurements were performed by the timecorrelated single-photon counting technique using apparatus that has been
described elsewhere [8], except that the excitation source was a mode-

293

locked, Q-switched Quantronix 416 Nd:YAG laser system which provided

80 ps pulses of 532 nm light with a frequency of 5 kHz. Lifetimes were
calculated by reiterative least-squares fitting with variable zero-time shift
between the instrument response function and measured decay curve.
Laser flash photolysis experiments were performed with a Quanta-Ray
DCR-1 Nd:YAG system to generate 532 nm (second harmonic) laser pulses
(a 6 ns pulse width). The experiments were performed in a rectangular
quartz cell of 6 mm path length with a right-angle configuration between the
directions of laser excitation and analyzing light. A typical experiment
consisted of a series of 5 - 10 replicate shots per single measurement, and the
average signal was processed with an LSI-11 microprocessor interfaced to a
PDP 11/55 computer.
Picosecond laser flash photolysis experiments were performed with a
mode-locked 532 nm laser pulse from Quantel YG-501DP Nd:YAG
(4 mJ, pulse width = 18 ps). The white continuum picosecond probe
pulse was generated by passing the residual fundamental output through
D,O-H_,O solution. The excitation and the probe pulse were incident on the
sample cell at right angles. The output was fed to a spectrograph (HR-320,
ISDA instruments, Inc.) with fiber optic cables and was analyzed with a dual
diode array detector (Princeton Instruments Inc.) interfaced with an IBM
AT computer. The delay in the probe pulse was introduced by varying the
length of the fiber optic cable. The details of the experimental set-up and its
operation are described in detail elsewhere [9]. The time zero in these
experiments corresponds to the time of maximum overlap of the probe and
excitation pulses.
Triplet quantum yields were determined with a 532 nm laser pulse as
the excitation source and zinc tetraphenylporphyrin in cyclohexane as the
standard (& = 1.0, E = 50 000 M-i cm-l at 470 nm) [lo] at non-saturating
laser intensities.

3. Results and discussion

and emission characteristics
3.1. Absorption
The absorption and emission spectra of PHNS+ in acetonitrile are given
in Fig. 1 and its excited state characteristics are summarized in Table 1. In
acetonitrile solutions PHNS+ exhibited absorption and emission maxima at
517 nm (e = 54 000 M-l cm-) and 560 nm respectively. A red shift in the
emission maximum was observed when the medium was changed to water.
The fluorescence quantum yield (&) and lifetimes (rr) in acetonitrile and
water are also given in Table 1. The fluorescence quantum yield of PHNS+ in
acetonitrile (& = 0.32) was higher than in water (& = 0.045). Since the
intersystem crossing efficiency is 10% or less, it is evident that a major
fraction of the singlet excited state undergoes a non-radiative decay. The
fluorescence decays were exponential and the values of rf were 930 ps in
water and 4.1 ns in acetonitrile respectively.

294

5-

-5

-4

)r
.c,

-3

c
H
-2

:
.+
w

--I

u
a

.
0

r
400

I
500

I
600

WAVELENGTH,
Fig. 1. Absorption and emission spectra (X,

I
700

nm
= 480 nm) of 10 ~_LM
PHNS+ in acetonitrile.

TABLE 1
Excited state characteristics of phenosafranin
In water

In CHaCN

520
595

517
560

Absorption maximum (Se-Sl) (nm)

Emission maximum (Sr-SO) (nm)
T-T absorption maximum (nm)
~PHNSH*+
3PHNS+

380,615
410,700

Fluorescence quantum yield

Triplet quantum yield
Fluorescence lifetime (ns)
Triplet ( 3PHNS+) lifetime (J&J)

0.045
0.06
0.93
19 (pH 7.5)

and 665
and 790

730,825
0.32
0.10
4.1
25

3.2. Picosecond laser flash photolysis

The excited singlet state (S,) absorption was studied by the picosecond
laser flash photolysis technique. The absorption spectra recorded at various
time intervals, following the 532 nm laser pulse (pulse width 18 ps) excitation of PHNS+ in water are shown in Fig. 2. The absorption spectra which
exhibited maxima at 430 nm and a negative absorption below 475 nm can
be attributed to the excited singlet (S1) absorption and ground state
depletion of PHNS+ respectively. As can be seen from the traces recorded in
Fig. 2, the decay of the absorption band (400 - 475 nm) matched well with
the recovery of the bleached dye. The lifetime of this transient as measured
from the decay of the absorbance at 430 nm was 980 ps. This value is in
good agreement with the value determined from the fluorescence decay
= 930 ps). This confirms our assignment of the 430 nm absorption band
(Tf

295

-0.24
400

425

450

475

WAVELENGTH,

500

525

nm

Fig. 2. Transient absorption spectra of aqueous PHNS+ solution

time intervals following 532 nm picosecond laser pulse excitation:
100 ps; curve c, 500 ps; curve d, 1 ns.

recorded at different
curve a, 0 ps; curve b,

-12
- IO
-8

400

500

600

WAVELENGTH,

700

800

nm

Fig. 3. Difference
(0)
and corrected (*) absorption spectra of PHNS+
(pH 4) recorded immediately after 532 nm laser pulse excitation.

(10 PM) in water

to the S1 state. The excited singlet state of rose bengal and erythrosin B has
similarly been characterized recently [ 91.
3.3. Triplet-triplet absorption spectra and decay kinetics
Nanosecond laser flash photolysis experiments were performed to
characterize the excited triplet state of PHNS+. The difference absorption
spectra and corrected absorption spectra in water at two different pH values
are shown in Figs. 3 and 4. The triplet excited state of PHNS+ exhibited
absorption maxima around 380, 615 and 665 nm in aqueous buffered

296

a
-5

-10
400

500

600

WAVELENGTH,
Fig. 4. Difference
(pH 8.5) recorded

700

800

nm

and corrected (*) absorption spectra of PHNS

immediately after 532 nm laser pulse excitation.
(0)

(10

/AM) in water

solutions of pH 1 - 6 and around 410, 700 and 790 nm in aqueous buffered

solutions of pH 7.5 - 9. Such a difference in the excited triplet state spectra
in acidic and alkaline aqueous solutions, which had been observed
previously by Chibisov et al. [5], can be attributed to the protonated and
unprotonated forms of excited triplet PHNS+. At higher alkalinity (pH > 10)
the production of radical anions of PHNS+ was also observed.
The difference extinction coefficients (Ae) of the triplet dye at different wavelengths were determined by the total depletion method [ll].
Absolute values of extinction coefficients were then determined from

Ah

CA

ICT+EAr

where exT and ehr are the extinction coefficients of triplet and ground state
PHNS+, AA^ is the absorbance difference at a given wavelength which was
recorded immediately after the flash, 1 is the path length and CT is the triplet
concentration.
The maximum extinction coefficients of the protonated form of triplet
PHNS+ in water were 11000 M-l cm- (380 nm), 9700 M-l cm-l (615 nm)
and 10 800 (665 nm). The unprotonated excited triplet has maximum
extinction coefficients of 8800 M- cm-l (410 nm), 6900 M- cm-l (700
nm) and 11600 M-l cm- (790 nm). The transient absorption spectrum of
3PHNS+ in acetonitrile (Fig. 5) was similar to the spectrum observed for the
unprotonated triplet in aqueous solutions. Absorption maxima were
observed at 730 nm (e = 13 100 M-l cm-) and 825 nm (E = 22 000 M-
cm-).
The absorbance differences (AA) recorded at different wavelengths
were found to decay with first-order kinetics. At a given pH the rate
constant for the decay of excited triplet PHNS+ was independent of wavelength. The observed lifetimes were 19 ps in water (pH 7.5) and 25 ps in
acetonitrile solution.

297

400

500

600

WAVELENGTH,

700

800

nm

Fig. 5. Difference (0) and corrected (*) absorption spectra of PHNS+ {lo FM) in acetonitrile recorded immediately
after 532 nm laser pulse excitation.
(Inset shows the decay
of the triplet absorption at 825 nm.)

3.4. Determination
of pK, of protonated
triplet phenosafranin
The transient absorption spectra of the triplet PHNS+ observed in acidic
and alkaline conditions indicate the existence of a protonation equilibrium
3PHNSH2+ eKa 3PHNS+ + H+

(2)

In all of the work reported here, ground state PHNS+ was in the unprotonated form (PHNS+) while the state of protonation of the triplet varied from
3PHNSH2+ to 3PHNS+. We employed the method used by Ohno et al. [12]
for the determination of the pK, of the protonated triplet excited state.
pH = pK, - log

[ 3PHNSH2+]
[ 3PHNS+]

(3)

The equilibration of triplet protonation was completed on the time scale of

the absorbance measurements. The plot of the maximum absorbance at
665 nm us. the pH of the medium (ionic strength p = 0.4) is shown in Fig. 6.
The inflection point of this plot gave pK, = 7.2. Similar values (7.3 + 0.2)
were also obtained when eqn. (3) was employed in the determination of pK,.
3.5. Quenching of triplet phenosafranin
The triplet absorption (825 nm) under 532 nm laser pulse excitation
was used to study the quenching of triplet PHNS+. In acetonitrile solutions
electron donors (D) such as triethylamine, diethylaniline and triphenylamine
were found to quench dye triplet with a net electron transfer

298

0.020

0.0

I5 -

zi
0.010

0.005

Fig. 6. Dependence of the maximum T-T absorption of PHNS

at 665 nm on the pH of
the aqueous medium (10 pM of PHNS* was excited with 532 nm laser pulse). The ionic
strength was maintained at 0.4 by adding KCl. (Error of measurement, +S%.)

3PHNS+ f D -

k,

PNHS + D

(4)

Rate constants for quenching by the amines were evaluated from the linear
dependence of the pseudo-first-order specific rates of decay on the concentration of the quencher (Fig. 7). As can be seen from Table 2, the values of
.lzsvaried from 2.8 X log M- s-r to 8.6 X lo9 M-l s-l and were close to the
value of a diffusion-controlled reaction.
The observed pseudo-first-order rate constant was also found to
increase with increasing ground state dye concentration. As cited previously
[5], this process can be attributed to the quenching of triplet by the ground
state dye molecules
3PHNS+ -t PHNS + -

PHNS + PHNS2+

(5)

The bimolecular rate constant for the self-quenching process (reaction (5))
was determined from the slope of the linear plot of kotid us. the concentration of PHNS+ (Fig. 7). Care was taken to excite only a fraction of the
ground state dye (less than 10%) in CH&N solutions. The net electron
transfer yield during this quenching process was very low in acidic aqueous
and acetonitrile solutions but was detectable in alkaline aqueous solutions.
The self-quenching rate constant in acetonitrile was determined to be 8 X
lOa M- s-l. The triplet lifetime obtained from the extrapolation of kd us.
[PHNS*] plot to zero concentration was 29 ps. Similar ground state quenching behavior has been noted previously for thiazine and oxazine dyes
[13,14].

299

01

20

30

40

50

60

70

80

IO

[Quencher],

90

FM

Fig. 7. Dependence of the pseudo-first-order rate constant of 3PHNS+ decay on the concentration of various quenchers in acetonitrile: curve a, diethyl aniline; curve b, triethylamine; curve c, PHNS+ (self-quenching). (Error of measurement, +5%.)
TABLE 2
Rate constants for the quenching of 3PHNS+ with various quenchers in acetonitrilea
Quencher

k, (~10~ M-r s-l)

Diethylaniline
Triethylamine
Triphenylamine
Oxygen
PHNS+ b

5.4
2.8
8.6
1.9
0.80

aTriplet decay was monitored from the absorption at 825 nm.

bRate constant for the self-quenching process.

3.6,

Singlet oxygen via photosensitization

It has been shown that dyes, such as thiazines and xanthenes, with a
strong absorption in the visible are important for singlet oxygen generation
[15]. Oxygen was found to quench the triplet excited state of PHNS+ in
aqueous and non-aqueous solutions
3PHNS+ + O2 --,

PHNS+ + 102*

(61

The bimolecular rate constant for the quenching of 3PHNS+ by O2 in acetonitrile was determined to be 1.91 X lo9 M-i s-. The quenching experiments

300

at various O2 concentrations
were performed by using solutions saturated
with 0,-N,
mixtures of known composition.
The oxygen concentrations
were calculated from the solubility of oxygen (1.9 mM) in air-saturated
acetonitrile [ 161. The production of 102* was further confirmed from its
reaction with 1,3_diphenylisobenzofuran
(DPBF) [15, 171 in laser flash
photolysis experiments.
3.7. Radical anion of phenosafrcsnin
As indicated in Section 3.5, quenching of triplet PHNS+ with amines
resulted in net electron transfer (reaction (4)). The spectral characteristics
of photochemically
generated semireduced
phenosafranin
(PHNS ) were
investigated in laser flash photolysis experiments. The transient absorption
spectrum recorded after 532 nm laser pulse excitation of PHNSf in acetonitrile containing triethylamine is shown in Fig. 8. PHNS exhibited maxima
at 440 nm (E = 29 000 M- cm-) and at 870 nm (E = 19 000 M-l cm-l).
Chibisov et al. observed similar absorption of the protonated and unprotonated forms of the semireduced phenosafranin in the 400 - 450 nm region
[5]. The long-wavelength
absorption
in Fig. 8 indicated that these semireduced radical anions were in the unprotonated form. The decay of PHNS
followed simple second-order kinetics with a rate constant close to the value
of a diffusion-controlled
reaction
(k = 1OO M- s-l). This decay was
attributed to the disproportionation
of PHNS
2PHNS -

400

PHNS+ + FHNS-

I,

500

(7)

600

700

800

WAVELENGTH,

nm

Fig. 8. Difference
absorption
spectrum of PHNS+ (10 PM) in acetonitrile containing
5 mM triethylamine.
The spectrum was recorded after the triplet decay (i.e. 5 /B after
532 nm laser pulse excitation).
The inset shows the decay of radical anion absorption at
440 nm.

301

The formation of leucodye (PHNS-) was confirmed from the steady state
photolysis of PHNS and triethylamine in acetonitrile.
Because of their interesting electroactive properties dyes, such as PHNS+,
are considered to be important in the photoelectrochemical
conversion and
storage of solar energy_ Preliminary results indicated that photoelectrochemical cells designed with PHNS+ as the photosensitizer exhibited a very
poor light energy conversion efficiency (<10-2%).
It has been shown that
microencaging
dyes with polymers modified their excited state properties
and made them more effective photosensitizers
in photoelectrochemical
cells [18,19].
Efforts are currently being made to employ PHNS+ dye in
polymeric hosts (e.g. nafion films) to improve the performance of photoelectrochemical devices [ZO] .
Acknowledgments
We would like to thank Dr. Maria Bohorquez
for her assistance in
fluorescence lifetime measurements and Dr. William E. Ford for confirming
the singlet oxygen
production
with luminescence
measurements.
The
research described herein was supported by the Office of Basic Energy
Sciences of the Department of Energy. This is Document No. NDRL-3143
from the Notre Dame Radiation Laboratory.
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