245

Luminescence, spectroelectrochemistry and photoelectrochemical

properties of a tetraruthenated zinc porphyrin

Koiti Araki and Henrique E. Toma

htituto de Quimica, Univmidade de SGo P&o, Caita Postal 20780, CEP 01498-970, Scio Paula, SP (Brazil)

(Received January 21, 1994, accepted February 22, 1994)

Abstract

We report the spectroelectrochemistry, luminescence and photoelectrochemical properties of a polymetallic complex

containing four [Ru(bipy),CI]+ groups attached to zinc-tetra(pyridyl)porphyrin (ZnTPyP). Six successive redox
states involving TPyP, ruthenium, zinc and bipyridine (bipy) species have been characterized spectroelectrochemicaliy
in the range - 1.8 to 1.7 V vs. a standard hydrogen electrode (SHE). The luminescence properties of the complex
in solution are centred on the porphyrin moiety. Fluorescence predominates at room temperature in solution,
whereas phosphorescence becomes very effective in the solid state or at low temperatures. In films, the peripheral
ruthenium groups exhibit antenna effects promoting efficient energy transfer to the porphyrin, and leading to
an enhanced photoclectrochemical response.

1. Introduction [l-3], since it exhibits electrochemically and pho-

tochemically active groups capable of interacting
In this work, we report the spectroscopic and via energy or electron transfer mechanisms, fa-
luminescence properties of a new polymetallic vouring the occurrence of enhanced photoelec-
species containing four [Ru(bipy),Cl] + groups trochemical properties.
(bipy, bipyridine) attached to theperipheralpyridine
N atoms of zinc meso-tetra(pyridyl)porphyrin
VnTqrP). _ 2. Experimental details

The [ZnTPyP{Ru(bipy)2Clj~](TFMS), - 3H,O

complex, where TFMS is the trifluoromethane-
sulphonate anion, was obtained by reacting
ZnTPyP and [Ru(bipy),Cl,] (1:4.1. molar ratio)
in glacial acetic acid, under reflux, and then in
‘. . methanol, as described in previous work on the
‘/
’\ related [TPyP{Ru(bipy),Cl},]Cl, complex [4]. The
I
latter can also be used as a starting reagent to
@ . obtain the zinc derivative, by refluxing with zinc(U)
acetate in methanol for 40 min. The chloride salt
was converted to the TFMS derivative by dissolving
in a minimum amount of methanol and precipi-
tatingwith an aqueous solution containing an excess
of LiTFMS. The product was collected on a filter,
w washed with water and dried under vacuum. Anal-
p-jMeso5,10,15,20-tetsa(pyridyl)porphyrin zinc(II)}tetrakis{bis- ysis: calculated for ZnRu,C,,H,,Nzs0,,S4F~*C~:
(bipyridine)chloride ruthenium(II)} ([ZnTPyP{Ru(bipy)zCl}~),14+ C, 47.6; H, 3.03; N, 10.7; found: C, 48.0; H, 3.05;
complex.
N, 10.4.
This tetraruthenated zinc porphyrin is partic- Cyclic voltammetry and spectroelectrochemical
ularly interesting as a model compound in artificial measurements were carried out as described pre-
photosynthesis and photoelectrochemical devices viously [4-61, using mirror-like finished platinum

1010.6030/94/$07.000 1994 Elsevier Science S.A. All rights reserved

SSDI 1010-6030(94)03821-B
246 K. Araki HE. Toma / Ptiofochemical pmpefiies of a !&amthenared zinc polphrrin

or glassy carbon (Tokai) disc electrodes. All po-

tentials are referred to the standard hydrogen
electrode (SHE). The electronic spectra were re-
corded on a Guided Wave model 260 fibre optics
spectrophotometer, or on a Hewlett Packard 8452A
diode array equipment. Fluorescence measure-
ments were carried out on a Photon Technology
(PTI) model LS-100 instrument, equipped with
near-IR-sensitive photomultipliers. The lumines-
cence properties in ethanol glass at 77 K were
obtained using a low-temperature accessory from
PTI and a quartz cell. Flash photolysis experiments
were performed with an Applied Photophysics
system consisting of a Nd/YAG SI.801 laser,
equipped with a harmonic generator. The argon-
saturated samples were pumped with the 355 nm
harmonic line (pulse width, 15 ns) and the decay
curves were recorded on a Tektronics model 2230
digital oscilloscope, interfaced with a microcom-
puter. Photoelectrochemical measurements were
carried out using a Princeton Applied Research
model 173 potentiostat attached to a quartz cell
with the conventional three-electrode arrangement
for cyclic voltammetry. In parallel, a photoexci-
tation system from Applied Photophysics was em-
ployed, consisting of a stabilized xenon lamp (150 Fig. 1. (A) Cyclic voltammograms of [ZnTPyP{Ru(bipy)z-
mW), a monochromator and a fibre optic cable. Cl},I(TFMS), (9.9X 10m4M) in DMF (0.10 MTEACIO,) obtained
The light intensities were calibrated using the using a platinum disc electrode. (B) Cyclic voltammograms of a
1.8 x 10-s mol c~~-~fiJrn adsorbedon a glassy carbon disc electrode
Guided Wave instrument in the light meter mode. in 0.026 M acetate buffer (pH 4.7) and 0.25 M LiTFMS. (TEA,
tetra ethylammonium ion).

3. Results and discussion

form, i.e. [Zn’ITPyP{Ru”(bipy),C1)414+. By scan-
The [ZnTPyP{Ru(bipy),Cl},14+ complex was iso- ning in the direction of more positive potentials,
lated and exhibited consistent analytical results. a strong reversible wave appears at 0.92 V, ex-
It was characterized in the solid state and in hibiting four times the intensity expected for a
solution, based on electronic absorption and fluor- single, monoelectronic redox species. This wave
escence spectroscopy, cyclic voltammetry and spec- is followed by an irreversible peak at 1.50 V. In
troelectrochemistry. All these techniques are very the cathodic region, two reversible waves can be
sensitive to the presence of impurities, such as detected at - 0.93 and - 1.14 V, followed by two
the starting reagents, and provide reliable evidence strong waves at - 1.35 and - 1.67 V. The latter
of the complex purity, as well as the proposed is reversible, and is responsible for the broad
composition. In contrast with the mononuclear signals above - 0.5 V observed in the reverse scan,
ZnTPyP species, the tetraruthenated porphyrin is indicating some decomposition of the complex
soluble in a variety of solvents, such as methanol, below - 1.6 V. In the range - 1.2 to + 1.2 V the
NJ+dimethylformamide (DMF), acetone and ace- complex is stable, yielding reversible waves in
tonitrile. Unfortunately, up to the present time, repetitive cyclic voltammograms.
we have not succeeded in obtaining suitable crystals The assignment of the redox processes in
for X-ray analysis. the tetraruthenated zinc porphyrin is not imme-
diate, because of the existence of at least four
3.1. Cyclic voltammetry and specfroelectro- redox active sites, which can exist in many succes-
chemistry sive oxidation states, i.e. Ru’~“‘“~ [7],
Typical cyclic voltammograms of the tetraruth- 2+/l -1/0/~1/-2 [~I, bipyO/-l/-Z [93 and Zn'V~O.
TPyP
enated complex in DMF solution are shown in In this case, spectroelectrochemical techniques are
Fig. 1. At 0 V, the complex is present in its original especially useful, providing direct evidence of the
redox sites involved, as well as the electronic the Rumnr redox couple, The fact that the four
interactions within the multibridged system, as a [Ru”(bipy),CI]+ groups are oxidized at the same
function of several oxidation states. potential is consistent with a weak coupling be-
The electronic spectrum of the [Zn”TPyP- tween the Ru”“” centres, as previously observed
{Ru”(bipy)zC1},]4 + complex shown in Fig. 2(A) for related polynuclear and polymeric systems
exhibits the characteristic absorption bands of [4-6,10,11].
Zn’TPyP at 430 nm (Soret band), 562 and 606 Above 1.5 V, the oxidation process leads to the
nm (Q bands), and of the [Ru”(bipy),Cl]+ moieties decay of the Soret and Q bands, with minor changes
at 298 nm (bipy, r--t@), 450-490 nm (Ru”-to- in the bipy n+r* transition, as can be seen in
bipy charge transfer (CT) envelope) and 358 run. Fig. 2(B). This is consistent with the oxidation of
The oxidation of the complex around l+O V is the porphyrin ring [12].
responsible for the complete decay of the metal- The reduction of the [Zn”TPyP{Ru”(bipy),-
to-ligand charge transfer (MLCT) bands in the CM”+ complex at -0.9 V leads to a systematic
450-490 nm region, splitting of the bipy r-+ ti bathochromic shift of the Soret and Q bands to
band at 298 nm into two peaks at 306 and 318 444 nm and 580 and 626 nm respectively, with a
nm with increased intensity and a bathochromic number of simultaneous isosbestic points, consis-
shift of the Soret band to 434 nm (Fig. 2(A)). tent with a well-behaved, reversible process in-
Based on the intensity of the corresponding elec- volving the Zn”TPyP moiety, as shown in Fig.
trochemical waves and on the dramatic changes 2(C). The spectroscopicchanges differ dramatically
in the electronic bands associated with the from those previously reported for the reduction
[Ru”(bipy),Cl] + moiety, the redox process ob- centred at the porphyrin ring, and are consistent
served at 0.92 V can be unequivocally ascribed to with a strong involvement of the metal centre in

2 ,050
._ .._...___________, ”

1.5

1
,”
2 0.5

$
Q 0

-1 ,500 V
1 /‘...........,s...
F

250 350 450 550 650 75a 250 a50 450 550 650 750

Wavelength (cm) Wavelength (cm)

Fig. 2. Spectroelectrochemistry of [ZnTPyP{Ru(bipy),Cl}.,](TFMS), (2.0 X 10m4 M) in DMF (0.10 M TEAClO4) at (A) D.XJ-I.05 V.
(B) 1.05-1.70 V, (C) 0.70 to -0.95 V, (D) -0.95 to -1.20 V, (E) -1.20 to -1.50 V and (F) -1.50 to -1.80 V.
248 K. draki, HE. Toma / Photochemical properties of a tetraruthenated zinc porphyrin

the reduced species [13]. In contrast, the second sponding to the singlet-singlet Q, and Qsl tran-
reduction process at -1.2 V leads to the decay sitions of the ZnTPyP group [15-171. It should
of the Soret and Q bands, and to the rise of new be noted that the excitation spectrum obtained
absorption,bands at 492 and 756 nm (Fig. 2(D)), by monitoring the intensity of these two fluor-
characteristic of a porphyrin rr radical anion [13]. escence emissions does not coincide with the ab-
At -1.5 V there is a pronounced decay of the sorption spectrum of the tctraruthenated complex,
bipy rr-+ r* band at 298 nm and of the band of but reproduces very closely the absorption profile
the zinc porphyrin r radical anion at 492 nm, with of the zinc porphyrin group, represented by the
the rise of new absorptions at 620 and above 800 Soret, QW and Q1, bands at 417, 554 and 601
nm (Fig. 2(E)), ascribed to the formation of co- nm respectively (Fig. 3(B)). In other words, there
ordinated bipy- radicals and porphyrin dianions. is no evidence of excitation of the porphyrin via
The electrochemical and spectroscopic changes the peripheral [Ru@ipy&l]+ groups, indicating
proceed in a irreversible way at - 1.8 V, as shown that the energy transfer from the peripheral groups
in Fig. 2(F), leading to the reduction of the second to the porphyrin centre is not efficient in solution
coordinated bipy l&and, as indicated by the dis- at room temperature. On the other hand, the lack
appearance of the MLCT and bipy r-+7$: bands of emission from the [Ru(bipy),Cl] + moieties sug-
at 490 and 298 nm respectively [14], and by the gests that the corresponding excited states arc
rise of a broad absorption band with a maximum rapidly deactivated in solution.
at 338 nm. At low temperatures (77 K), the emission spec-
trum of the corresponding ethanol glass exhibits
narrower Q,,, and Q,, bands at 597 and 652 nm
3.2. Luminescence properties of the polymetnllic respectively, and another band at 770 nm (Fig.
complex in solution 3(C)). This new band can be ascribed to the triplet
The room temperature excitation and emission state emission (T,) by comparison with the phos-
spectra of the tetraruthenated zinc porphyrin in phorescence emission of similar porphyrins [15-171.
argon-saturated ethanol are shown in Figs. 3(A) The excitation spectrum obtained by monitoring
and 3(B). The complex exhibits two well-defined the 652 nm porphyrin singlet emission is similar
fluorescence bands at 606 and 655 nm, corre- to that at room temperature (Fig. 3(D)); however,
when the 770 nm porphyrin triplet emission is
monitored, a quite different excitation profile re-
sults (Fig. 3(E)). In this case, the charge transfer
absorptions associated with the peripheral ruthe-
nium complexes also appear around 500 and 450
nm, indicating the occurrence of an energy transfer
process from the [Ru(bipy)&l(PyP)]+ triplet ex-
cited states to the lowest energy triplet state of
the porphyrin. This conclusion is corroborated by
the fact that the emission spectrum obtained on
excitation at 450 nm, i.e. in the MLCT band of
the ruthenium complexes, exhibits essentially the
porphyrin phosphorescence emission (Fig. 3(F)).
The emission bands of the [Ru(bipy),Cl(L)]+
complexes, where L is pyridine or 4-acetylpyridine
[18], occur at 660 and 653 nm respectively. By
comparison, we presume that the emission band
of the peripheral [Ru(bipy),Cl(PyP)]+ complexes
should appear around 660 nm. In fact, a broad,
weak band is observed at 680 nm (Figs. 3(C) and
3(F)) in the tetraruthenated porphyrin. So, the
600 700 800 excited state energy level of the [Ru(bipy)&l(L)] +
moieties is lower than that of the porphyrin singlet
Fig. 3. Emission (h-=422 nm) (A) and excitation (A,,=655 nm) states precluding a direct energy transfer to these
spectra of an 8X lo-’ M ethanol solution of [ZnTPyP{Ru(bipy)Z-
CI}J(TFMS), at room temperature. Emission (A,,=422 nm) (C),
states.
excitation (h,, = 655 nm) (II), excitation (A,,=778 nm) (IX) and The two types of excitation profile (Figs. 3(D)
emission (A., = 450 nm) (F) spectra of a 2x 10 -6 M glassy ethanol and 3(E)) observed at 77 K indicate that two
solution at 77 K. mechanisms are responsible for the population of
 K Araki, H.E. Toma I Photochemical properties of a tetraruthenated zinc porphyrin 249

-0.05 J 8 I
450 500 550 600 650 700 750
Wavelength (nm)
Fig. 4. &cited state differential spectrum of 1.5~10~~ M of
[ZnTPyP(Ru(bipy)zCl}$& in aqueous solution (AcX=355 nm).

the low-lying triplet state of ZnTPyP: one involving

singlet-triplet intersystem crossing within the por-
phyrin, and another, involving direct energy trans-
fer from the ruthenium excited state to the triplet
state of the zinc porphyrin group. At low tem-
peratures, in a glassy matrix, the expected decrease
in the rates of thermal relaxation processes for
the ZnTPyP and [Ru(bipy)&J(PyP)]+ excited
states should favour the parallel, unimolecular
400 500 600 700 600
photophysical processes, increasing the quantum Wavelength (nm)
yields of intersystem crossing and energy transfer Fig. 5. (A) Electronic spectrum nf a film deposited on the surface
within the polymetallic complex. of a platinum electrode. (B) Photocurrent (average of five mea-
The nature of the excited states was also in- surements) spectrum of a 5.9X IO-’ mol cm-’ film of [Zn-
vestigated using flash photolysis at room temper- TPyP{Ru(bipy),Cl},](TFMS), adsorbed onto a glassy carbon elec-
trode in an 02-saturated aqueous solution containing 0.26 M
ature (A,,=355 nm; pulse width, 15 ns). The decay
acetate buffer (pH 4.7) and 0.25 M LiTFMS at E=0.22 V. (C)
curves were rigorously fitted by a single-exponential Excitation (A,, =725 nm) and emission (A,.=422 nrn) spectra
function, leading to an average lifetime of 0.9 + 0.1 of [ZnTPyP(Ru(bipy)zC1},](TFMS)~ film on glassy carbon at room
,us. From the decay curves, the time-resolved dif- temperature.
ferential spectrum of the tetraruthenated por-
phyrin was obtained, as shown in Fig. 4. The adsorbed films as can be inferred from its char-
spectrum is very similar to those previously re- acteristic electronic spectrum (Fig. 5(A)) and elec-
ported in the literature for the triplet excited states trochemical response (Fig. l(B)).
of related porphyrins [19], confirming that the low- The cyclic voltammograms of the films exhibit
lying excited state of the polymetallic system is reversible waves at 0.95 V (Fig. l(B)) associated
centrcd on the zinc porphyrin moiety. with the Ru”‘~’ redox pair. The linear dependence
observed for the peak currents with respect to the
3.3. Spectroscopic and photoelectrochemical scan rates and the aspect of the sine-shaped waves
properties of the complex adsorbed in films are characteristic of strongly adsorbed films [20].
The [ZnTPyP{Ru(bipy),Cl}~](TFMS), .3H,O In contrast with the fluorescence emission ob-
complex is not soluble in aqueous solution and served for the complex in solution at room tem-
forms strongly adsorbed films on glassy carbon perature, the films exhibit only a narrow emission
surfaces by the slow evaporation of a methanol band at 730 nm, as found in the phosphorescence
solution. The amount of porphyrin can be con- spectrum in ethanol glass at 77 K. A remarkable
trolled by transferring precise volumes of the meth- point is that no fluorescence emission is observed
anol solution onto the electrode surface. A typical for the films at room temperature (Fig. 5(C)). The
film distribution containing 5X lo-’ mol cm-’ excitation spectrum parallels the absorption pro-
would consist of approximately 600 monolayers, files of the ZnTPyP and [Ru(bipy),CI]* moieties,
assuming a molecular area of 400 A”. The nature indicating that the peripheral groups are effectively
of the polymetallic complex is preserved in the acting as antennae in the complex. This means
2.50 K. Araki, H.E. Toma / l’horochemical pmperties ofa tetrancthenoted
that, in contrast with the photophysical behaviour
in solution, there is an efficient electronic coupling
between the peripheral and central groups in the
films. Presumably, the expected restrictions from
orthogonal orbital overlap between the peripheral
and central groups are removed by conformational
changes and packing effects in the solid, leading
to more effective spin-orbit coupling. Conse-
quently, a much faster singlet-triplet conversion
and a decrease in the fluorescence quantum yield
are expected. The stronger electronic interaction
between both sites in the films also promotes a
rapid energy transfer rate from the [Ru*(bipy)ZC1+]
groups towards the zinc porphyrin moiety, com-
peting with thermal deactivation processes.
Another remarkable aspect associated with the
photoactivity of the ZnTJ?yP and [Ru(bipy),Cl]+
moieties in the films is illustrated by their pho-
toelectrochemical properties, as shown in Fig. S(B).
When the adsorbed films are illuminated in an
aqueous solution containing dissolved dioxygen and
the electrolyte LiTFMS, a stable photocurrent
response (Fig. 5(B)) is generated, reproducing the
absorption profile (Fig. 5(A)) of the solid tetra-
ruthenated complex. This result confirms that the
[Ru(bipy),Cl]+ groups can effectively act as an-
tennae, absorbing light and transferring energy or
electrons within the molecular framework at the
electrode surface. The starting species is regen-
erated in the presence of dissolved dioxygen, in
a catalytic manner, so that the process can be
repeated indefinitely as long as dioxygen is supplied
to the solution.
The mechanisms involved in the photoelectro-
chemical behaviour, and the contrasting photo-
chemical properties of the complex in solution and
in immobilized systems, are interesting aspects in
this work and deserve further investigation. For
this reason, a detailed study on the properties and
zinc porphyrin
applications of these photoconductive films is being
carried out in our laboratory.
Acknowledgments
We gratefully acknowledge the financial support
from FAPESP, CNPq and PADCT, and the help
of Professors M. Politi and L.H. Catallani in the
flash photolysis experiments.
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