Porphyrin dyes for TiO2 sensitization

Fabrice Odobel,*a Errol Blart,a Marie Lagrée,a Monique Villieras,a Hamada Boujtita,b
Nabil El Murr,b Stefano Caramoric and Carlo Alberto Bignozzi*c
a
Laboratoire de Synthèse Organique, UMR 6513 CNRS, Faculté des Sciences et des
Techniques de Nantes, B.P. 92208, 2, rue de la Houssinière, 44322 Nantes cedex 3, France.
E-mail: odobel@chimie.univ-nantes.fr
b
Laboratoire d’Analyse Isotopique et Electrochimique de Métabolismes, UMR 6006, Faculté
des Sciences et des Techniques, B.P. 92208, 2, rue de la Houssinière, 44322 Nantes cedex 3,
France
c
Dipartimento di Chimica, Università di Ferrara, Via L. Borsari, 46, 44100 Ferrara, Italy

Received 30th November 2002, Accepted 16th January 2003

First published as an Advance Article on the web 30th January 2003

A series of six new free base porphyrins were synthesized for use as photosensitizers in TiO2 dye-sensitized
photo-electrochemical cells. The porphyrin sensitizers are attached to the TiO2 photoelectrode by phosphonic
or carboxylic acid anchoring groups. These anchoring groups were placed on different substitution positions on
the porphyrin moiety. The new dyes were fully characterized by absorption and emission spectroscopies,
electrochemistry and photo-electrochemical spectroscopy. The photo-electrochemical performances of the
sensitizers are discussed and compared to the known 5,10,15,20-tetra(4-carboxyphenyl)porphyrin sensitizer. In
this study, we show that the nature of the anchoring group (phosphonic or carboxylic acids) has little impact
on the photo-electrochemical performance of the cell. However, the substitution position of the anchoring
group on the porphyrin strongly influences the monochromatic photon-to-electron conversion efficiency of the
resulting cell. The results indicate that the electronic coupling of this type of dye with the d-band of the
semiconductor is one of the key parameters in the design of efficient sensitizers.

Introduction goal, the series of porphyrins 1–7, shown in Fig. 1, were

Dye sensitization of porous thin films of wide band gap
semiconductors (e.g. TiO2, SnO2, ZnO) is an attractive research
field in view of its considerable technological implications for
photovoltaic energy.1,2 In this area, much effort has been
focused on dye molecules based on metal polypyridine
complexes and their analogues.2–5 The development of organic
sensitizers, exhibiting performances similar to those observed
for the metal complexes, is also considered of interest, both
from the point of view of economic dye production as well as
for the acquisition of information regarding the factors
controlling the efficiency of photo-electrochemical solar cells.
It is indeed striking to observe that, so far, only the com-
bination of metal polypyridine complexes and TiO2 produces
efficient solar cells.
In past years, a number of organic dyes, such as
phthalocyanines,6–9 perylene bis-amides,10–12 xanthenes,13–15
hemicyanines16–18 and porphyrins19–23 have been tested as
sensitizers, but the light-to-electricity conversion efficiency is
rather modest compared to that shown by metal polypyridine
complexes.4,5,7,24,25 At present, it is still unclear why these dyes
have limited performance and the reported photocurrent
efficiencies for classes of homologous species differ widely in
value. For example, Grätzel and co-workers,26,27 Wamser and
Cherian,20 and Durrant et al.28 achieved monochromatic
photon-to-electron conversion efficiency (IPCE) values of up
to 80% with porphyrin sensitizers, while others such as
Durantini et al.22 and Koehorst et al.19 reported lower
performances with similar or identical dyes (maximum IPCE
12%).
In view of the valuable photochemical and electrochemical
properties of porphyrins and of their low cost of production,
we embarked on a study aimed at elucidating the factors which
limit their efficiency in solar cells based on nanocrystalline
TiO2. In this study, which represents a first step towards this
prepared and tested. In the synthetic design, we have
introduced modifications at the molecular level in order to
verify the possible influence of structural and thermodynamic
parameters on the IPCE of sensitized solar cells. Special
attention was given to the type of binding between the sensitizer
and semiconductor, provided either by carboxylate or phos-
phonate anchoring groups, and to the substitution position of
these anchoring groups on the porphyrin ring. These modifi-
cations are expected to affect the cell performance through
changes in the electronic coupling between the sensitizer and
the semiconductor conduction band.
We report here the synthesis of new porphyrin dyes and the
characterization of their spectroscopic, electrochemical, photo-
physical and photo-electrochemical properties.
Experimental
General methods
1
H NMR spectra were recorded on an ASPEC Bruker 200
spectrometer. Chemical shifts are referenced relative to residual
protium in the deuterated solvent (CDCl3 7.26 ppm, CD3OD
4.5 ppm). The peak assignments are given as follows: chemical
shifts with the number of protons involved and multiplicity of
the signal (s singlet, d doublet, t triplet, m multiplet) in
parentheses. UV-Visible absorption spectra were recorded on
Shimadzu UV-2401PC and Perkin Elmer Lamba 40 spectro-
photometers. Fast atom bombardment mass spectroscopic
(FAB-MS) analyses were performed in meta-nitrobenzyl
alcohol matrix on a ZAB-HF-FAB spectrometer. Cyclic
voltammetry was conducted with a MacLab model ML160
potentiostat-galvanostat controlled by resident software
(Echem v1.5.2 for Windows). Solutions for measurements in
0.1 M Bu4NPF6 in dichloromethane were approximately 2 mM
before use and were purged with argon in a three-electrode cell.

502 J. Mater. Chem., 2003, 13, 502–510 DOI: 10.1039/b210674d

This journal is # The Royal Society of Chemistry 2003
 Fig. 1 Structures of the porphyrin sensitizers studied in this work.
In all the measurements, the working electrode was platinum,
with a platinum wire as the auxiliary electrode. Potentials are
referenced to a saturated calomel electrode (SCE). In all the
experiments, the scan rate was 100 mV s21. Steady-state
luminescence studies were performed using a Yvon Spex
Fluoromax 2 spectrofluorimeter equipped with a Hamamatsu
R3896 tube. Solid thin films were excited at 33u. Emission
lifetimes were measured using a PRA system 3000 time-
correlated single photon counting apparatus equipped with a
Norland model 5000 MCA card and a hydrogen discharge
pulsing lamp (50 kHz, half-width 2 ns). The decays were
analyzed by means of Edinburgh FLA 900 software. Photo-
electrochemical measurements were performed in a two-
electrode sandwich cell arrangement. Typically, 10 ml of
electrolyte (0.3 M TBAI/0.03 M I2 in acetonitrile) was
sandwiched between a TiO2 photoanode and a counter
electrode. Pt-sputtered conductive glass was employed as the
counter electrode. The cell was illuminated with a 150 W Xe
lamp coupled to an Applied Photophysics high irradiance
monochromator. The irradiated area was 0.5 cm2. Light
excitation was through the fluorine-doped tin oxide (FTO)
glass (ca. 10 V cm2, LOEF) substrate of the photoanode.
Photocurrents were measured under short circuit conditions
with a Kontron model DMM 4021 digital electrometer.
Incident irradiances were measured with a calibrated silicon
photodiode from UDT Technologies.
Thin layer chromatography (TLC) was carried out on
aluminum sheets precoated with Merck 5735 Kieselgel
60F254. Column chromatography was performed on Merck
5735 Kieselgel 60F (0.040–0.063 mm mesh). Air-sensitive
reactions were carried out under argon in dry solvents and
glassware. Chemicals were purchased from Aldrich and used as
received. (4-Formylphenyl)phosphonic acid diethyl ester
(11),29,30 (3-formyl- phenyl)phosphonic acid diethyl ester
(12),29,31 4,4’-diethyl-3,3’-dimethyl-2,2’-dipyrrylmethane (19),32
5-phenyl-2,2’-dipyrrylmethane (18),33 5,10,15-tris(3,5-di-tert-
butylphenyl)porphyrin34,35 and 5,10,15,20-tetrakis(4-phospho-
natophenyl)porphyrin (2)29,30 were prepared according to
literature methods.
Photoanode preparation36
TiO2 colloid solutions were prepared by hydrolysis of titanium
isopropoxide, Ti{OCH2(CH3)2}4: 50 mL of titanium isoprop-
oxide (Fluka) were added dropwise, by means of an addition
funnel, to 300 mL of deionized water acidified with 2.1 mL of
HNO3 65% under vigorous stirring. During the hydrolysis, a
white precipitate formed. The mixture was stirred for 8 h at
J. Mater. Chem., 2003, 13, 502–510 503
80 uC. During this process, the mixture was allowed to
concentrate to 120 mL, corresponding to a TiO2 concentration
of 170 g L21. A stable colloidal sol resulted from this
procedure. The size of the colloidal particles was ca. 8 nm
and X-ray diffraction analysis showed them to consist of
anatase. 50 mL of this solution were heated at 220 uC for 12 h in
an autoclave. During this process, the nanoparticles grew to
50–100 nm in size. After cooling at room temperature, 3 g of
Carbowax 2000 (Aldrich) were added to the resulting gel and
the mixture was stirred at room temperature for 8 h. FTO
conductive glass was covered on two parallel edges with 3M
adhesive tape (ca. 20 mm thick) to control the thickness of the
TiO2 film. The colloid was applied to one edge of the substrate
and distributed with a glass rod sliding over the tape-covered
edges. After air drying, the electrode was heated in an oven at
450 uC for 30 min in the presence of air. The resulting film
thickness was of the order of 6–7 mm.
Porphyrins 1–3, 5 and 6 were dissolved in 8 : 2 CH2Cl2–
CH3OH solutions containing 20 mM sodium taurodeoxycho-
late and adsorbed overnight at room temperature on the
corresponding photoanodes. In all cases, ca. 1023 M solutions
of the porphyrins were used. The solubility of porphyrin 3 was
improved in the presence of 0.01 M CF3COOH. Porphyrins
4 and 7 were adsorbed from ethanolic solutions. After dye
adsorption, the photoanodes were soaked for 5 min in a ca.
0.01 M solution of triethylamine in diethyl ether, then rinsed
with CH2Cl2 and CH3OH, and dried.
5,10,15,20-Tetrakis(3-phosphonatophenyl)porphyrin octaethyl
ester (14)29
A solution of 12 (2 g, 8.3 mmol) and pyrrole (0.55 mL, 8 mmol)
in 30 mL of propionic acid was refluxed in a flask protected
from light for 2 h. The mixture was evaporated to dryness, and
purified by column chromatography on neutral alumina eluting
with dichloromethane–methanol (98.5 : 1.5). Yield: 33%. 1H
NMR (200 MHz, CDCl3): d 22.78 (s, 2H, NH); 1.42 (t, 24H,
CH3); 4.40 (q, 16H, CH2); 7.93 (m, 4H, Hm of C6H4); 8.29 (dd,
4H, Hp of C6H4); 8.42 (m, 4H, Ho of C6H4); 8.68 (m, 4H, Ho
and Hm of C6H4); 8.83 (s, 8H, Hb of pyrrole). FAB1-MS: m/z
calcd. for C60H66N4O12P4 1158.4; found 1159.4 (M 1 H1).
5,15-Bis(4-phosphonatophenyl)-10,20-diphenylporphyrin
tetraethyl ester (15)29
A solution of 11 (272 mg, 1.13 mmol) and 18 (250 mg,
1.13 mmol) in 5 mL of propionic acid was refluxed in a flask
protected from light for 30 min. The mixture was evaporated to
dryness and purified by flash chromatography eluting with
dichloromethane–methanol (98.5 : 1.5). Yield: 31%. 1H NMR
(200 MHz, CDCl3): d 22.79 (s, 2H, NH); 1.51 (s, 12H, CH3);
4.42 (q, 8H, CH2); 7.78 (m, 6H, Hm,p of C6H5); 8.26 (m, 12H,
4Ho of C6H5 and 8H of C6H4); 8.79 (d, 4H, Hb of pyrrole);
8.87 (d, 4H, Hb of pyrrole). FAB1-MS: m/z calcd. for
C52H48N4O6P2 886.3; found 887.3 (M 1 H1).
Porphyrins 16 and 17
A round-bottom flask fitted with a rubber septum was charged
with freshly distilled acetonitrile (320 mL) and purged with
bubbling argon for 20 min. Then, the aromatic aldehyde, either
11 or 12 (1 g, 3.5 6 1023 mol), was added, along with 19
(885 mg, 3.8 6 1023 mol). The stirring and bubbling with
argon was continued for an additional 30 min, then,
trifluoroacetic acid (540 ml) was added via syringe in one
portion. The reaction mixture was stirred for 17 h at room
temperature, resulting in a dark red solution. A solution of
2,3-dichloro-5,6-dicyanobenzoquinone (1.2 g, 5.3 6 1023 mol)
in 60 mL of toluene was then added in one portion and the
mixture refluxed for 30 min. The solvent was evaporated to
dryness and the crude mixture was purified by flash
504 J. Mater. Chem., 2003, 13, 502–510
chromatography eluting with dichloromethane–ethanol
(99 : 1).
5,15-Bis(4-phosphonatophenyl)-2,8,12,18-tetraethyl-3,7,13,17-
tetramethylporphyrin tetraethyl ester (16). Yield: 80%. 1H
NMR (200 MHz, CDCl3): d 22.42 (s, 2H, NH); 1.52 (t,
12H, CH3CH2); 1.77 (t, 12H, CH3CH2); 2.45 (s, 12H, CH3);
4.00 (q, 8H, CH3CH2); 4.4 (dq, 8H, CH3CH2); 8.22 (m, 8H,
C6H4); 8.36 (s, 2H, Hmeso). FAB1-MS: m/z calcd. for
C52H64N4O6P2 902.4; found 903.4 (M 1 H1).
5,15-Bis(3-phosphonatophenyl)-2,8,12,18-tetraethyl-3,7,13,17-
tetramethylporphyrin tetraethyl ester (17). Yield: 82%. 1H
NMR (200 MHz, CDCl3): d 22.30 (s, 2H, NH); 1.36 (t,
12H, CH3CH2); 1.80 (t, 12H, CH3CH2); 2.45 (s, 12H, CH3);
4.01 (m, 8H, CH3CH2); 4.31 (m, 8H, CH3CH2); 7.88 (m, 2H,
Hm of C6H4); 8.26 (d, 2H, Ho of C6H4); 8.42 (m, 2H, Hp of
C6H4); 8.58 (d, 2H, Ho and Hm of C6H4); 10.26 (s, 2H, Hmeso).
FAB1-MS: m/z calcd. for C52H64N4O6P2 902.4; found 903.4
(M 1 H1).
General procedure for hydrolysis of phosphonate ester groups
In a round-bottom flask, the porphyrin (0.1 mmol) and
bromotrimethylsilane (0.5 mL, 3.8 mmol) in 20 mL of dry
DMF was heated under argon atmosphere at 60 uC for 24 h.
The solvent was evaporated under vacuum and the green solid
residue was dissolved in methanol and stirred at room
temperature for 1 h. Diethyl ether was added until precipitation
occurred, and the resulting solid was filtered off, washed with
diethyl ether and dried under vacuum. The crude product was
purified by column chromatography over Sephadex gel LH20
eluting with dichloromethane–methanol (80 : 20).
1. Yield: 92%. 1H NMR (200 MHz, CD3OD and CDCl3): d
22.47 (s, 2H, NH); 1.66 (t, 12H, CH3CH2); 2.42 (s, 12H, CH3);
3.94 (q, 8H, CH3CH2); 7.93–8.08 (m, 8H, H of C6H4); 8.42 (s,
2H, Hmeso). Anal. calcd. for C44H48N4O6P2?7.2H2O: C 58.78, H
6.97, N 6.25; found C 58.68, H 7.02, N 6.32%.
3. Yield: 94%. 1H NMR (200 MHz, DMSO-d6 and
CD3OD): d 22.5 (s, 2H, NH); 7.83 (m, 6H, Hm,p of C6H5);
8.12 to 8.29 (m, 12H, 4Ho of C6H5, 8H of C6H4, 8H, Hb of
pyrrole); 8.82 (s, 4H, OH). Anal. calcd. for
C44H32N4O6P2?7.4H2O: C 59.78, H 5.30, N 6.34; found C
59.52, H 5.21, N 6.21%.
5. Yield: 98%. 1H NMR (200 MHz, CD3OD and CDCl3): d
22.08 (s, 2H, NH); 1.48 (t, 12H, CH3CH2); 2.11 (s, 12H, CH3);
3.67 (m, 8H, CH3CH2); 7.94 (m, 2H, H5 of C6H4); 8.31 (m, 2H,
H4 of C6H4); 8.39 (s, 2H, H9 of C6H4); 8.60 (m, 2H, H2
of C6H4); 10.23 (s, 2H, Hmeso). Anal. calcd. for
C44H48N4O6P2?8.3H2O: C 59.78; H 5.30; N 6.34; found C
59.68; H 5.22; N 6.19%.
6. Yield: 92%. 1H NMR (200 MHz, CD3OD): d 23 (s, 2H,
NH); 6.76 to 6.84 (m, 16H, C6H4); 7.51 (s, 8H, Hb of pyrrole);
7.54 (s, 8H, OH). Anal. calcd. for C44H34N4O12P4?8.3H2O: C
50.99; H 4.89; N 5.11; found: C 50.90; H 4.82; N 5.03%.
[5,10,15-Tris(3,5-di-tert-butylphenyl)porphyrinato]copper(II)
(20)
A round-bottom flask was charged with 5,10,15-tris(3,5-di-tert-
butylphenyl)porphyrin (180 mg, 0.21 mmol), copper acetate
(30 mg, 1.6 mmol), 50 mL of dichlomomethane and 20 mL
of methanol. The mixture was refluxed for 30 min, and the
progress of the reaction was followed by TLC. The crude
reaction mixture was washed with water and the organic layer
decanted and dried over MgSO4. After solvent evaporation, the
crude red solid was purified over silica gel eluting with hexane–
dichlomomethane (95 : 5). Yield 95%. FAB1-MS: m/z calcd. for
C62H72N4Cu 935.5; found 935.5 (M1).
[5-Formyl-10,15,20-tris(3,5-di-tert-butylphenyl)porphyrinato]-
copper(II) (21)
A 25 mL three-necked round-bottom flask, equipped with a
condenser, a thermometer, a dropping funnel and a drying
tube, was charged at 0 uC with 5 mL of dichloromethane and
0.3 mL of DMF. The mixture was stirred for 2 min at 0 uC and
0.4 mL of POCl3 was added dropwise. The mixture was stirred
for 15 min at 0 uC. After formation of the Vilsmeier complex, a
solution of the copper porphyrin 20 (110 mg, 1.17 6 1024 mol
in 10 mL of dichloromethane) was added dropwise. Alter
complete addition of the porphyrin, the solution was heated for
2 h at 45 uC. The mixture was cooled with an ice-water bath and
a saturated solution of sodium acetate in water (100 mL)
added. The mixture was heated at 75 uC for 1 h, the phases were
separated and the aqueous phase extracted with dichloro-
methane. The organic phase was washed several times with
water, concentrated with a rotary evaporator and filtered
through neutral alumina. The crude product was purified by
column chromatography eluting with dichloromethane–hexane
(20 : 80). Yield: 98%. UV-Vis (CH2Cl2) lmax/nm: 425, 546, 597.
Since the copper(II) in porphyrin 21 prevents its 1H NMR
spectrum being collected, a sample was demetalated for
analysis (see below).
Scheme 1 Synthetic routes for preparation of the porphyrins.
General procedure for demetalation of copper porphyrins 21 and
23
The copper porphyrin (3 6 1025 mol) was dissolved in 5 mL of
sulfuric acid. The mixture was stirred for 15 min, then, the
crude product was poured onto crushed ice (50 mL), treated
with a 10% aqueous solution of Na2CO3 and the mixture
washed with dichloromethane. The organic layer was decanted
and dried over MgSO4, concentrated with a rotary evaporator
and filtered through neutral alumina. The crude product was
purified by column chromatography on silica gel.
22. Yield 69%. Column chromatography eluting with
dichloromethane–hexane (20 : 80). 1H NMR (200 MHz,
CDCl3): d 21.83 (s, 2H, NH); 1.53 (s, 54H, tBu); 7.8 (s, 3H,
Hp); 8 (s, 6H, Ho); 8.76 (dd, 4H, Hb of pyrrole); 9 (d, 2H, Hb of
pyrrole); 10 (d, 2H, Hb of pyrrole); 12.51 (s, 1H, CHO). FAB1-
MS: m/z calcd. for C63H74N4O 902.6; found 903.6 (M 1 H1).
8. Yield: 72%. Column chromatography eluting with
dichloromethane–methanol (90 : 10). 1H NMR (200 MHz,
CDCl3): d 22.88 (s, 2H, NH); 1.51 (s, 18H, tBu’); 1.53 (s, 36H,
t
Bu); 7.28 (t, 1H, H’p); 8.06 (t, 2H, Hp); 8.87 (d, 2H, H’o); 8.99
(d, 4H, Ho); 8.97 (s, 4H, Hb of pyrrole); 9.01 (d, 2H, Hb of
pyrrole); 9.71 (d, 2H, Hb of pyrrole); 9.85 (s, 1H, CO2H).
FAB1-MS: m/z calcd. for C63H74N4O2 918.6; found 919.6
(M 1 H1).
J. Mater. Chem., 2003, 13, 502–510 505
 Scheme 2 Reagents and conditions: (i) POCl3, DMF (yield 88%); (ii) TFA–H2SO4, RT (yield 90%); (iii) KMnO4, acetone (yield 80%).
[5-Carboxy-10,15,20-tris(3,5-di-tert-butylphenyl)porphyrinato]-
copper(II) (23)
Formyl porphyrin 21 (1.9 6 1025 mol) was dissolved in 10 mL
of acetone and 0.2 mL of water, and KMnO4 (1.5 eq, 4.5 mg,
2.86 6 1025 mol) was added. After complete solubilization of
the reagents, the solution was heated for 2 h at 55 uC. The
mixture was concentrated and the crude product was purified
by column chromatography over silica gel eluting with
dichloromethane–methanol (90 : 10). UV-Vis (CH2Cl2) lmax/
nm: 416, 540, 600. FAB1-MS: m/z calcd. for C49H68N4O2Ni,
802.5; found 803.5 (M 1 H1).
Results and discussion
Synthesis of the porphyrin sensitizers
The preparation of tetraaryl-meso-porphyrins 1329,30 and
1429,31 is based on the classical condensation of pyrrole with
aldehydes 11 and 12, respectively, under Adler conditions
(Scheme 1).37 The trans-porphyrins 15,29 16 and 17 were
synthesized via the MacDonald [212] condensation38,39 of the
(5-phenyl)dipyrrylmethane 1833,40 and the diethyl(dimethyl)-
dipyrrylmethane 1932 with the phosphonate-functionalized
benzaldehydes 11 and 12. Note that quite high yields (80%)
Fig. 2 Absorption spectrum of porphyrin 7 in dichloromethane (full
line) and on a TiO2 electrode (dashed line). The inset shows an
expansion of the 500–700 nm region.
506 J. Mater. Chem., 2003, 13, 502–510
were obtained with the more electron-rich 19, reacted in
acetonitrile in the presence of TFA.
The porphyrin 7, bearing the carboxylic acid anchoring
group directly on the porphyrin macrocycle, was obtained in
three steps (Scheme 2). First, a formylation was accomplished
in reasonable yield by a Vilsmeyer–Haack reaction applied to
copper porphyrin 20.41–43 In the second step, the aldehyde
group was oxidized to carboxylic acid by potassium perman-
ganate. Finally, the metal decomplexation of the copper
porphyrin was carried out using the very acidic mixture
TFA–H2SO4 (Scheme 2).
Electronic absorption spectra
The absorption spectra of the porphyrins were recorded in
dichloromethane solution and on TiO2 electrodes. Fig. 2 and 3
show the absorption spectra of porphyrins 7 and 2, taken as
examples, and the relevant spectral features and molar
extinction coefficients of porphyrins 1–7 are reported in
Table 1.
The spectra of the free base porphyrins exhibit an intense
Soret or B-band around 410 nm, assigned to a p–p* transition
to the second electronic excited state,44 and four Q-bands
between 500 and 650 nm, corresponding to p–p* transitions to
the first electronic excited state. In the Gouterman four orbital
models,45 these transitions arise predominantly from the two
Fig. 3 Absorption spectrum of porphyrin 2 in dichloromethane (full
line) and on TiO2 electrode (dashed line).
Table 1 Absorption properties of the porphyrins in dichloromethane–methanol (95 : 5) for 1–7 and in pure dichloromethane for TPP and
ethioporphyrin

Soret band, l/nm (e/105 M21 cm21) Q-bands, l/nm (e/104 M21 cm21)

1 408 (1.8) 507 (0.12) 540 (0.39) 573 (0.49) 624 (0.10)
2 418 (2.7) 515 (1.2) 550 (0.56) 590 (0.38) 645 (0.27)
3 418 (1.1) 515 (1.0) 550 (0.46) 590 (0.31) 645 (0.23)
4 419 (1.8) 516 (1.6) 550 (7.2) 590 (0.47) 647 (0.22)
5 409 (1.1) 507 (1.4) 540 (0.52) 574 (0.63) 625 (0.22)
6 420 (1.0) 515 (1.2) 550 (0.60) 590 (0.39) 646 (0.34)
7 418 (2.9) 516 (1.1) 550 (0.70) 590 (0.35) 647 (0.28)
TPPa 421 (5.1) 519 (1.4) 553 (1.1) 592 (0.50) 648 (0.61)
Ethioporphyrinb 422 (2.2) 518 (1.6) 553 (0.82) 592 (0.51) 648 (0.46)
a
TPP: 5,10,15,20-tetraphenylporphyrin. bEthioporphyrin: 5,15-diphenyl-8,12,18,22-tetraethyl-7,13,17,23-tetramethylporphyrin.

nearly degenerate excited configurations [alu(p),eg(p*)] and
[a2u(p), eg(p*)].44,45
In solution, the absorption maxima of the porphyrins 1–7 are
similar to those of the corresponding TPP and ethioporphyrins
without anchoring substituents (Table 1). This can be attrib-
uted to the fact that the meso-aryl substituents are perpendi-
cularly oriented to the porphyrin macrocycle, thus interrupting
the p-conjugation between these two groups. As a result, the
anchoring groups in porphyrins 1–7 have very little electronic
interaction with the porphyrin p-orbitals. In the adsorbed film,
the band maxima are slightly blue shifted with respect to the
solution, a feature which can be ascribed to the increase of
polarity from dichloromethane to the TiO2 surface as well as to
partial porphyrin aggregation and to excitonic coupling
between the chromophores.46,47
Upon porphyrin adsorption on TiO2 electrodes, the color of
the film tends to turn green, indicating that the pyrrole
nitrogens strongly interact with the hydroxylic groups present
at the surface of the semiconductor. This is confirmed by the
absorption spectrum, which displays two Q-bands due to the
new D4h symmetry of the porphyrin. Deprotonation was
achieved by soaking the electrode in a dilute solution of
triethylamine in diethyl ether. The films coated with the
porphyrin dyes showed absorbances of 2–3 on the Soret band
and y1 on the Q-bands, displaying quite a large light
harvesting efficiency between 400 and 700 nm (Fig. 2 and 3).
an electrochemically inactive support since the energy level of
the conduction band is sufficiently high to prevent electron
injection from the porphyrin excited state (flat band potential
of the conduction band of ZrO2 is located at 22.02 V vs. SCE).2
Fig. 4 shows the emission spectra of porphyrin 2 adsorbed on
TiO2 and ZrO2. Relevant photophysical data for the investi-
gated porphyrins are reported in Table 2. The two fluorescence
bands observed are assigned to relaxation from the zero and
hot vibronic levels of the lowest singlet excited state S1. For all
porphyrin dyes, the fluorescence intensities are reduced on
TiO2 substrates relative to ZrO2; however, there is still some
unquenched fluorescence, which indicates that the electron
injection yield is far from being complete (Fig. 4).
The exact quantification of the fluorescence quenching is
difficult to establish due to variation in the dye loading on the
ZrO2 and TiO2 electrodes, and to different electrode transmit-
tances. Qualitatively, however, the results are in agreement
with those reported by Grätzel and co-workers26,27 and
Koehorst et al.,19 who observed incomplete fluorescence
quenching of their porphyrin sensitizers. The energy level of
the singlet porphyrin excited state can be determined from the
emission maxima of the shortest wavelength emission
(Table 2). The energy of the singlet excited state is a little
higher for octaalkylporphyrins 1 (1.95 eV) and 5 (1.91 eV) as a
consequence of the inductive effect of the alkyl chains raising
the energy of the LUMO.

Steady-state fluorescence
Fluorescence spectra of the porphyrin were recorded on TiO2
and ZrO2 electrodes. The ZrO2 electrode can be considered as
Cyclic voltammetry
For solubility reasons, the electrochemical measurements were
performed in dichloromethane solutions containing the
phosphonate ester derivatives of porphyrins 1–3, 5 and 6.
Similar CV waves were observed in the other cases, with
anodic–cathodic peak splittings (Epa 2 Epc) of the order of
100–160 mV, indicating slow electron transfer. The half-wave
potentials are summarized in Table 3, together with the
maximum monochromatic photon-to current conversion
efficiencies (see next section). Upon oxidation, the product
formed is a p-cation radical, delocalized on the porphyrin
macrocycle;48,49 the oxidations of octaalkylporphyrins 1 and 5
are less anodic due to the inductive effect of the alkyl
substituents. Excited-state oxidation potentials, obtained

Table 2 l1 and l2 fluorescence emission maxima for porphyrin dyes

adsorbed on TiO2 electrodes

1 2 3 4 5 6 7

l1/nm 630 655 660 675 650 670 660

l2/nm 694 725 720 725 698 720 720
E00/eV 1.96 1.89 1.87 1.84 1.91 1.88 1.88
t/ns 0.3 8.2 3.1 10 9 4.4 4.2
E00 ~ spectroscopic energy level of the singlet porphyrin excited
state; t ~ emission lifetime, measured in 8 : 2 CH2Cl2–CH3OH for
Fig. 4 Fluorescence spectra of porphyrin 2 on ZrO2 (full line) and on porphyrins 1–3, 5 and 6, and in C2H5OH for 4 and 7.
TiO2 (dashed line).

J. Mater. Chem., 2003, 13, 502–510 507

Table 3 Redox and photo-electrochemical properties of the porphyrin
sensitizers

E1/2/V vs. Max IPCE on

SCE Epa 2 Epc/V E*ox/V vs. SCE Soret band (%)

1 0.87 0.13 21.09 9

2 1.13 0.16 20.76 8
3 1.04 0.12 20.83 5
4 1.10 0.10 20.74 10
5 0.86 0.12 20.90 21
6 1.08 0.11 20.80 8
7 1.06 0.13 20.79 17

from the standard equation E*ox ~ E1/2 2 E00, are also
reported in Table 3.
Photo-electrochemical properties
The performance of the porphyrin sensitizers has been studied
in a regenerative photo-electrochemical cell using I32/I2 as
electron mediators in acetonitrile.36 The photocurrent action
spectra of the porphyrin dyes are shown in Fig. 5, where the
incident monochromatic photon-to-current conversion effi-
ciencies (IPCE) values are plotted as a function of the
excitation wavelength. The IPCE(l) is defined by eqn. 1.
1:24|103 (eV nm)|Photocurrent density(mA cm{2 )
IPCE(l)~ (1)
Wavelength(nm)|Photon flux(mW cm{2 )
The photoaction spectra were observed to closely match the
corresponding absorption spectra of the adsorbed dyes. The
highest efficiency was achieved on the most intense Soret band,
with maximum IPCE values around 20%.
If the reflective losses of the transparent nanocrystalline
electrode are neglected, the IPCE of the photovoltaic cell can
be expressed as the product of three key parameters: the light
harvesting efficiency (LHE), the electron-injection yield (winj)
and the electron collecting efficiency (g) in the external circuit
(eqn. 2, Scheme 3).
IPCE ~ LHE 6 winj 6 g (2)
The fact that IPCE values lower than 21% were obtained on
the Soret band, where the optical density of the photoanode is
higher than 2.5, allows us to exclude the role of LHE in the low
photovoltaic performance of the cell.
Fig. 5 Photocurrent action spectra of the sensitizers 1–8 recorded in a
sandwich cell. The inset shows an expansion of the 450–700 nm region.
Scheme 3 Schematic representation of the different reactions occuring
at the TiO2 photoelectrode surface: CB is the conduction band; kfluor is
the rate constant of the fluorescence deactivation of the porphyrin
excited state; kinj is the rate contant of the photoinduced electron
transfer from the porphyrin excited state; kCR is the rate contant of the
charge recombination between the oxidized porphyrin and electrons in
the CB; kreg is the rate contant of the electron-transfer reaction between
the oxidized porphyrin and the iodide in the electrolyte.
The g term is essentially controlled by two parameters: (i) the
rate of iodide oxidation by the oxidized porphyrin after
electron injection (kreg) and (ii) the rate of charge recombina-
tion (kCR) of the oxidized porphyrin with the conduction band
electrons (Fig. 3). kreg Can not be considered a limiting factor
because the ground-state oxidation potentials of the porphyrins
are more positive than those of the best dyes that yield very
high IPCEs.2 Considering the redox potential of the I2/I32
redox couple (0.2 V vs SCE),50 the free energy of the latter
electron-transfer reaction is energetically favorable with these
porphyrin dyes (2DG w 0.5 eV). The charge recombination
reaction is known to be slow with ruthenium polypyridine
sensitizers and this is rationalized by the fact that electronic
interactions between the negative charge (electron in TiO2) and
the positive charge (hole on ruthenium metal) are weak because
the two charges are insulated by the bipyridine ligands.2 With
porphyrin sensitizers, this feature does not exist, therefore, the
charge recombination process ought to be faster than in
ruthenium complexes. However Durrant et al. have recently
reported that the rate of charge recombination between
conduction band electrons and oxidized porphyrin sensitizers
is in the range of several milliseconds.23 This rate is sufficiently
slow to permit the regeneration of the ground state of the
porphyrin by the iodide in solution. As a result, it seems
reasonable also to exclude g as a factor limiting the IPCE
obtained with these porphyrins dyes. The remaining factor
controlling the IPCE is the electron-injection quantum yield
(winj), which directly depends on the electron-injection rate
(kinj). The low IPCE can be certainly attributed to a low
electron-injection yield, because a residual fluorescence emis-
sion was detected upon adsorption of the dye on TiO2 (Fig. 4).
This suggests that the radiative process competes with the
electron injection, thus decreasing the branching ratio between
these two deactivation channels (kfluor versus kinj). The kinetics
of the electron-transfer process can be analyzed according to
the Marcus theory framework. This model states that the
factors controlling the electron-transfer rate are: the free energy
change, the reorganization energy associated with the inter-
facial electron transfer and the electronic coupling between the
electron donor and the acceptor. The reorganization energy
may not be a limiting factor for these sensitizers, since it is
known not to be larger than that of ruthenium polypyridine
complexes; it is on the order of 0.4 eV for a large macrocycle
such as a porphyrin in a polar solvent.51,52 The free energy
associated with the electron injection may play a role in the rate
of the electron injection, because the best sensitizer (porphyrin
5) is among those having the highest excited-state oxidation
potentials. In the case of porphyrins 2–4, 6 and 7, charge
injection could be activated53 due to their low excited-state

508 J. Mater. Chem., 2003, 13, 502–510

oxidation potentials. Moreover, the excited-state reducing
ability of porphyrins 1 and 5 is comparable to that of the more
efficient ruthenium polypyridine complexes,5,24,25 known to
give IPCE values of the order of 90%, as a consequence, it
seems logical to assume that the electronic coupling between
the porphyrin excited state and the d-band of the semicon-
ductor plays a key role. The importance of electronic coupling
to the efficiency of electron injection is convincingly demon-
strated by the IPCE variations between porphyrins 7 and 4.
Although these two porphyrins exhibit quite similar excited-
state oxidation potentials and similar absorption and emission
characteristics (Tables 1, 2 and 3), they lead to very different
IPCE values (Fig. 5). Porphyrin 7 bears the COOH anchoring
group directly on the p-aromatic core. This feature certainly
allows for a stronger electronic interaction with TiO2 compared
to porphyrin 4, in which the remote COOH groups are
electronically decoupled from the porphyrin macrocycle.
The sensitivity of the IPCE to the substitution position of the
phosphonate anchoring groups in porphyrins 1 and 5 is also
remarkable. This can be interpreted as due to differences in the
orientation and distance of the dye with respect to the TiO2
surface imposed by the directionality of the anchoring groups.
The porphyrin that bears phosphonic acid groups in meta
positions on the phenyl ring (dye 5) may lie closer to the TiO2
surface than that with para substituents (dye 1). Consequently,
these variations may bring about significant differences in the
magnitude of the electronic coupling. Activated electron
transfer for dyes 2 and 6 can explain why the IPCE values of
these sensitizers are the same and do not parallel the differences
observed between dyes 1 and 5. The injection quantum yield of
the former sensitizers might be limited by the lower excited-
state potentials.
Finally, at can be noted that replacement of the phosphonic
with the carboxylic functions, as in the case of 2 and 4, doesn’t
seem to modify the dye photo-electrochemical performances.
This can be explained by the fact that both dyes are
electronically decoupled from TiO2 because the meso-aryl
groups orient perpendicularly to the porphyrin macrocycle.
In conlusion, the synthesis of the various porphyrin
sensitizers can be achieved in a few steps with relatively high
yields. The substitution position of the anchoring groups
strongly influence the IPCE of the resulting cell. More
importantly, it was shown that the electronic coupling of this
type of dyes with the semiconductor is certainly one of the key
parameters for the design of efficient sensitizers in this class of
compounds.
Acknowledgements
We thank Dr Daniel Maume for mass spectrometry (LDH,
Ecole Vétérinaire of Nantes) and CNRS for financial support.
S. C. and C. A. B. acknowledge financial support from
Consorzio Spinner contract no. 574/01.
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53 Intense emissions are observed from the adsorbed porphyrin dyes,
indicating that charge injection from the excited dyes to the
conduction band is not efficient. This fact can be related to low
charge injection rates, resulting from the presence of an activated
barrier to the interfacial electron-transfer process. All experiments
510 J. Mater. Chem., 2003, 13, 502–510
were, in fact, carried out in the presence of tetrabutylammonium
iodide, which has no stabilizing effect on the conduction band and
may leave the flat band at a potential more negative than the
excited-state oxidation potential of the investigated dyes
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1994, 98, 6195). Experiments with Li1 ions, which have a
stabilizing effect on the conduction band, indicated, on the
other hand, a direct interaction between Li1 and the porphyrin
nitrogens similar to that produced by protonation, with a
consequent increase in the oxidation potential, emission red
shift and a decrease in the photo-electrochemical performance.