A new approach to N-phenylquinolino[2,3,4-at]porphyrins: Electrochemical and photochemical studies

Article abstract of DOI:10.1142/S108842461100346X

A new route to N-phenylquinolino[2,3,4-at]porphyrins is described and the electrochemical and photochemical properties of the synthesized derivatives were investigated. The electrochemical studies (cyclic voltammetry and rotating disk voltammetry) of the

Full text of DOI:10.1142/S108842461100346X

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2011; 15: 575–582
DOI: 10.1142/S108842461100346X
Published at http://www.worldscinet.com/jpp/
A new approach to N-phenylquinolino[2,3,4-at]porphyrins.
Electrochemical and photochemical studies
Ana M.V.M. Pereiraa,b, Maria G.P.M.S Nevesa, José A.S. Cavaleiro*a,
Jean-Paul Gisselbrechtb, Christophe Jeandonb and Romain Ruppert*b
a Department of Chemistry and QOPNA, University of Aveiro, 3810-193 AVEIRO, Portugal
b Institut de Chimie, UMR 7177 du CNRS, Université de Strasbourg, 67000 STRASBOURG, France
Dedicated to Professor Karl M. Kadish on the occasion of his 65th birthday
Received 15 March 2011
Accepted 27 April 2011
ABSTRACT:AnewroutetoN-phenylquinolino[2,3,4-at]porphyrinsisdescribedandtheelectrochemical
and photochemical properties of the synthesized derivatives were investigated. The electrochemical
studies (cyclic voltammetry and rotating disk voltammetry) of the free-base and the corresponding Ni,
Cu and Pd complexes have shown that the presence of the phenyl group is responsible for the formation
of stable radical cations. The capacity of the N-phenylquinolino[2,3,4-at]porphyrins to generate singlet
oxygen was evaluated and some of them have promising features as photosensitizers.
KEYWORDS: π-extended porphyrin, Ullmann conditions, cyclic voltammetry, photosensitizer, singlet
oxygen generation.
[8–12]. In a simpler approach, the meso aryl groups
already present in the molecule can be fused to the por-
phyrin macrocycle. This last strategy can be repeated from
one up to four times, because there are four meso posi-
INTRODUCTION
The synthesis of extended π-conjugated molecules is
still a very active field of research [1]. In the particular
case of porphyrins, due to their chemical and physical
properties, these extended aromatic molecules might
tions available. These reactions have been widely used to
introduce functionalities between pyrrole β-positions and
be useful in areas such as photodynamic therapy [2],
meso aryl groups [13–16].
two-photon absorption [3], nonlinear optics [4] or pho-
In this article, we describe the electrochemical proper-
tovoltaics [5]. Therefore, several research groups have
focused on the synthesis and chemical transformation of
ties of N-phenylquinolino[2,3,4-at]porphyrin H2-4 and of
the corresponding complexes M-4 (M = Cu, Ni and Pd)
porphyrins into new derivatives with improved features
(Chart 1). Their ability to generate singlet oxygen was
that may turn them into possible candidates for different
estimated from the oxidation of cholesterol through UV-
applications.
vis and NMR techniques. These porphyrinic complexes
Among the available synthetic tools for porphyrin
can be obtained by metalation of the known H2-4 [15c].
functionalization [6], fusion of aromatic rings with the
Additionally, an alternative and easier route to those
porphyrin nucleus [7] is the most obvious way to extend
N-phenylquinolino[2,3,4-at]porphyrins, involving modi-
the molecule. This can be achieved intermolecularly
fied Ullmann amination conditions, is also reported.
by directly adding aromatic rings to the porphyrin core
EXPERIMENTAL
SPP full member in good standing
The 1H NMR spectra were recorded at 300 MHz with
a Bruker 300 spectrometer. CDCl3 was used as solvent.
The chemical shifts (δ) are expressed in parts per million
*Correspondence to: José A.S. Cavaleiro, email: jcavaleiro@
ua.pt, tel: +351 234370717 and Romain Ruppert, email:
rruppert@unistra.fr, tel: +33 (0)3-68-85-17-00
Copyright © 2011 World Scientific Publishing Company

576
A.M.V.M. PereIrA et al.
2 equiv.) in dimethylsulfoxide (3 mL) was heated under
argon at 90 °C for 4 h. After cooling, addition of dichlo-
romethane and several washings with water, the solvent
was evaporated and the residue was purified by chro-
matography on silica gel (eluent: cyclohexane/dichlo-
romethane 2/3). Crystallization from dichloromethane/
methanol afforded Ni-4 as a green solid in 66% yield
(39.9 mg).
Ph
N
N
N
N
M
Ph
Ph
N
Demetalation of Ni-4. To a solution of Ni-4 (82 mg,
110 µmol) in trifluoroacetic acid (1.5 mL) was added con-
centrated sulfuric acid (1.5 mL). After 45 min of vigor-
ous stirring, the reaction mixture was poured on ice and,
after addition of dichloromethane, neutralized with a sat-
urated aqueous solution of sodium hydrogenocarbonate.
The organic phase was then washed twice with water and
dried on sodium sulfate. Filtration through a short silica
gel column and crystallization from dichloromethane/
methanol afforded H2-4 as a green solid, identical to a
pure sample [15c], in almost quantitative yield (78 mg).
UV-vis (CH2Cl2): λmax, nm (ε, M-1.cm-1) 413 (151500),
453 (81900), 594 (20300), 612 (19900), 665 (17700).
Preparation of Cu-4. To a solution of H2-4 (27 mg,
39 µmol) in toluene (20 mL) was added Cu(OAc)2 (10
mg, 57 µmol, 1.5 equiv.). This reaction mixture was
refluxed under argon for 19 h. The solid residue obtained
after evaporation of the toluene was then filtered through
a short alumina column (eluent: cyclohexane/dichlo-
romethane 1/1). Crystallization from dichloromethane/
methanol afforded the green solid Cu-4 in 92% yield (28
mg). UV-vis (CH2Cl2): λmax, nm (ε, M-1.cm-1) 405 (76000),
458 (168400), 563 (10100), 606 (14400), 637 (29700).
HRMS (ESI): m/z 764.1872 (calcd. for CuC50H31N5 [M]•+
764.1870).
Ph
H2-4, M = 2H
Ni-4, M = Ni
Cu-4, M = Cu
Pd-4, M = Pd
Chart 1. Structures of the synthesized N-phenylquinolino-
[2,3,4-at]porphyrins 4
(ppm) and the coupling constants (J) in Hertz (Hz). The
HRMS (ESI) were determined with a MicrOTOF Q
spectrometer. The UV-vis spectra were recorded with a
Agilent 8453 diode-array spectrophotometer in CH2Cl2.
Chromatographic separations were performed with silica
gel (Merck, 230–400 mesh) or alumina (Merck, 70–230
mesh). Analytical TLC was carried out on precoated
sheets with silica gel (0.2 mm thick, Macherey-Nagel).
Dichloromethane and toluene were distilled from cal-
cium hydride and from sodium metal, respectively. All
other solvents and reagents were used without further
purification.
Synthesis
Theknownnickel(II)complexesNi-3[15c]andNi-5[15a]
were prepared according to previously published
procedures.
Preparation of Pd-4. A solution of H2-4 (27 mg,
39 µmol) and Pd(acac)2 (19 mg, 62 µmol, 1.6 equiv.) in
toluene (20 mL) was refluxed under argon for 40 h. After
evaporation of the toluene, filtration through a short alu-
mina column (eluent: cyclohexane/dichloromethane 1/1)
and crystallization from dichloromethane/methanol, the
green Pd-4 was isolated in 95% yield (30 mg). 1H NMR
(300 MHz; CDCl3; 50 °C): δΗ, ppm 7.54 (1H, dd, J =
8.5 and 1 Hz, cyclized Ph), 7.61–7.92 (16+1H, m, H-Ph
and H-3), 8.05–8.08 (2H, m, Hortho-Ph), 8.12–8.16 (2H,
m, Hortho-Ph), 8.20–8.23 (2H, m, Hortho-Ph), 8.63 (1H, d,
J = 5.1 Hz, β−pyrr), 8.71 (1H, d, J = 5.1 Hz, β−pyrr),
8.70–8.73 (2H, m, β−pyrr), 8.93 (1H, d, J = 5.3 Hz,
β−pyrr), 9.38 (1H, dd, J = 8.5 and 1 Hz, cyclized Ph), 9.72
(1H, d, J = 5.3 Hz, β−pyrr). UV-vis (CH2Cl2): λmax, nm
(ε, M-1.cm-1) 409 (112700), 446 (98000), 467 (111300),
527 (6800), 552 (9900), 594 (17700), 627 (33000).
HRMS (ESI): m/z 807.1631 (calcd. for PdC50H31N5 [M]•+
807.1609).
Preparation of Ni-4. A solution of Ni-3 [15c] (83.4 mg,
110 µmol) in nitrobenzene (5 mL) was refluxed for 19 h.
After cooling, the reaction mixture was poured on the
top of a silica gel column, and the nitrobenzene was
eluted with cyclohexane. The reaction products were
then eluted using a 2/3 mixture of cyclohexane/dichlo-
romethane. Crystallization from dichloromethane/meth-
anol afforded Ni-4 as a green solid in 79% (65.8 mg).
1H NMR (300 MHz; CDCl3; 50 °C): δΗ, ppm 7.43 (1H, dd,
J = 8.0 and 1 Hz, cyclized Ph), 7.52–7.82 (16+1H, m,
H-Ph and H-3), 7.89–7.92 (2H, m, Hortho-Ph), 7.96–8.00
(2H, m, Hortho-Ph), 8.03–8.06 (2H, m, Hortho-Ph), 8.53
(1H, d, J = 5.0 Hz, β−pyrr), 8.58–8.61 (2H, m, β−pyrr),
8.61 (1H, d, J = 5.0 Hz, β−pyrr), 8.85 (1H, d, J = 5.0
Hz, β−pyrr), 8.96 (1H, dd, J = 7.7 and 1 Hz, cyclized
Ph), 9.48 (1H, d, J = 5.0 Hz, β−pyrr). UV-vis (CH2Cl2):
λ
max, nm (ε, M-1.cm-1) 426 (140800), 454 (sh, 118700),
556 (3100), 601 (19500), 633 (34000). HRMS (ESI): m/z
759.1913 (calcd. for NiC50H31N5 [M]•+ 759.1927).
Alternative preparation of Ni-4. A solution of Ni-5
[15a] (54.7 mg, 80 µmol), iodobenzene (33 µL, 88 µmol,
1.1 equiv.), CuI (1.5 mg, 8 µmol, 0.1 equiv.), L-proline
(1.9 mg, 16 µmol, 0.2 equiv.) and K2CO3 (22.1 mg, 160 µmol,
Photochemical tests
Using a slide projector lamp (250 W), light was filtered
by passing through an aqueous potassium dichromate
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solution (λ > 510 nm). A solution of the chromophore
internal standard and are uncorrected from ohmic drop.
The spectroelectrochemistry was carried out with a home-
made electrochemical cell fitted with a thin part allowing
recording of the electronic spectra. The working electrode
was a platinum grid located in the thin part of the cell.
(10-5 M) and cholesterol (2 × 10-3 M) in benzene (20 mL)
was irradiated for 4 h at room temperature. The porphy-
rin decomposition was evaluated by comparison of the
initial and final electronic spectra of the solution. After
1
evaporation of the benzene and drying, the H NMR
spectrum was recorded in CDCl3 and the amount of oxi-
dized cholesterol was determined by integration of the
olefinic protons of the product resulting from the ene
reaction vs. cholesterol. The initial cholesterol/sensitizer
ratio being equal to 200, the turnover number is defined
as the number of moles of cholesterol oxidized per mole
of sensitizer.
RESULTS AND DISCUSSION
Synthesis
The N-phenylquinolino[2,3,4-at]porphyrin H2-4 was
initially obtained by a synthetic route developed by some
of us, involving the following steps: (i) β−pyrrolic nitra-
tion of the 5,10,15,20-tetraphenylporphyrin with cop-
per nitrate [17, 18], (ii) synthesis of the corresponding
Ni complex, after demetalation of the copper derivative,
(iii) reduction of the nitro group with tin powder to
affordthe(2-amino-5,10,15,20-tetraphenylporphyrinato)-
nickel(II) [18], (iv) arylation of this amine with bro-
mobenzene using Buchwald-Hartwig conditions, (v)
demetalation and (vi) cyclization in nitrobenzene [15c].
Herein, it was verified that the final cyclization reac-
tion might also be performed starting directly from the
nickel complex Ni-3 (Scheme 1, route a), giving the Ni-4
porphyrin in excellent yield (79%).
Electrochemical studies
The electrochemical measurements were carried out in
CH2Cl2 containing 0.1 M Bu4NPF6 in a classical three-
electrode cell by cyclic voltammetry (CV) and rotating-
disk voltammetry (RDV). The working electrode was a
glassy carbon disk (3 mm in diameter), the auxiliary elec-
trode a Pt wire, and the pseudo reference electrode a Pt
wire. The cell was connected to an Autolab PGSTAT30
potentiostat (Eco Chemie, Holland) driven by a GPSE
software running on a personal computer. All potentials
are given vs. Fc/Fc+ (ferrocene/ferrocinium) used as
Ph
NH2
HN
Pd(OAc)2, rac-BINAP
N
N
N
N
N
N
N
N
Sn/HCl
PhBr, KOtBu
Ni
Ph
Ni
Ph
Ph
Ph
CHCl3, rt
toluene, 100 °C, N2
route a
79%
69%
Ph
Ph
Ni-2
Ni-3
NO2
PhNO2
reflux
N
N
N
Ni
Ph
Ph
79%
N
Ph
H
Ph
N
Ni-1
N
CuI, L-proline
PhI, K2CO3
route b
N
N
N
N
N
N
N
P(OEt)3
Ni
Ph
Ni
Ph
Ph
Ph
o-Cl2C6H4, 155 °C
DMSO, 90 °C
N
74%
66%
Ph
Ph
Ni-5
Ni-4
Scheme 1. Preparation of the nickel porphyrin Ni-4
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578
A.M.V.M. PereIrA et al.
C8H17
C8H17
PS, O2, hν
HO
HO
OOH
Scheme 2. Cholesterol oxidation by singlet oxygen
Knowing that the treatment of the easily
accessible (2-nitro-5,10,15,20-tetraphenylpor-
phyrinato)nickel(II) 1 with triethyl phosphite
is a very efficient route to prepare the nickel(II)
complexNi-5[15a](Scheme1,routeb),prompt-
ed us to examine the possibility of using this
compound as starting material to obtain N-phe
nylquinolino[2,3,4-at]porphyrins. The desired
Ni-4 porphyrin was obtained under Ullmann
amination conditions [19], by adding copper
iodide, L-proline, potassium carbonate [20] and
iodobenzene to a solution of Ni-5 in dimethyl-
sulfoxide. Heating this mixture for 4h afforded
in a rather good yield (66%) the expected Ni-4
fused derivative (see Scheme 1, route b). Using
this alternative approach, Ni-4 can be prepared
in only two steps, just as efficiently as by the formerly
published procedure [15c]. All attempts to obtain Ni-4
using the previous Buchwald-Hartwig amination reaction
conditions [Pd(II) + rac-BINAP + base] for the arylation
of the secondary amine (formally an enamine) Ni-5 were
unsuccessful.
Fig. 1. Electronic spectra of H2-4 and Pd-4
The results of these experiments are summarized in
Table 1. 5,10,15,20-Tetraphenylporphyrin (H2TPP) was
used as the reference compound. The palladium complex
Pd-4 (entry 5: 56 turnovers in 4 h of irradiation) was
an excellent singlet oxygen generator when compared
to H2TPP (entry 1: 12 turnovers in 4 h of irradiation).
Moreover, Pd-4 is highly stable under irradiation condi-
tions, as shown by the fact that its electronic spectrum
taken after irradiation was superimposable with the start-
ing spectrum. Even after 8 h of irradiation, only 8% of
decomposition was detected and the turnover number
was 104. The results with the copper complex Cu-4
are comparable with those obtained for the reference
H2TPP. The nickel complex Ni-2, as expected, was pho-
tochemically inactive. The free-base H2-4 (entry 2) was
found to be three times more active than the reference
H2TPP; however, H2-4 was less stable than its metallo
counterparts under similar irradiation conditions (20% of
decomposition after 4 h of irradiation).
The demetalation of Ni-4 by treatment with a trif-
luoroacetic acid/sulfuric acid solution for less than 1h
gave the free-base H2-4 in almost quantitative yield. This
free-base was then metalated by standard methods [21],
affording the desired Pd-4 and Cu-4 complexes in very
good yields.
Photochemical experiments
Since compounds 4 absorb strongly at wavelengths
higher than 600 nm (see Fig. 1), we checked their effi-
ciency to generate singlet oxygen by using cholesterol
oxidation as a test reaction (see Scheme 2) [22].
Table 1. Photochemical oxidation of cholesterol by different chromophores
Chromophore
λ
max (ε in benzene)
Turnover numbera
(after 4 h of irradiation)
% chromophore
decomposition
H2TPP
H2-4
648 (3400)
665 (23000)
632 (39000)
636 (37000)
626 (39000)
12
31
0
< 2
20
Ni-4
< 1
< 3
< 4
Cu-4
Pd-4
12
56
Experimental conditions: 20 mL benzene, 2 × 10-3 M cholesterol, 10-5 M chromophore, 250 W (λ >
a
510 nm), 4 h of irradiation, cholesterol/chromophore = 200. The turnover number is defined as the
number of moles of cholesterol oxidized per mole of sensitizer.
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Table 2. Cyclic voltammetry data for the N-phenylquinolino[2,3,4-at]porphyrin derivatives 4 and Ni-5a
Compound
E°red2
E°red1
E°ox1
E°ox2
E°ox3
E°ox1–E°red1
Ni-4
H2-4
Cu-4
Pd-4
Ni-5c
-2.17 (85)b
-1.98 (70)b
-2.15 (90)
-2.12 (90)
-2.04
-1.78 (70)
-1.65 (60)
-1.79 (70)
-1.71 (60)
-1.64
0.16 (75)
0.17 (75)
0.14 (70)
0.24 (60)
0.32
0.57 (75)
0.47 (60)
0.53 (90)
0.65 (60)
0.63
1.15 (90)
1.94
1.82
1.93
1.95
1.96
1.20
a
Measured in dichloromethane containing 0.1 M Bu4NPF6. Potentials are given vs. the couple Fc/Fc+ and
in parentheses the peak separation at 0.1 V/s. See Experimental section for details. b Reversible if rate > 2 V/s.
c Taken from Ref. 15a.
Electrochemical studies
to the oxidation of Ni(II) to Ni(III), but it was difficult to
confirm this spectroscopically due to the proximity to the
solvent’s oxidation (see Fig. 2). Reversible one-electron
transfers were observed, except for the second reduction
step of H2-4 and Ni-4. At these very cathodic potentials,
the generated dianions might react with protons (from
residual traces of water present in solution).
At higher scan rates, a reversible behavior was
observed, indicative of a chemical follow-up reaction at
lower scan rates. The Pd-4 potential values are anodically
shifted, when compared with those of Ni-4 and Cu-4. In
fact, for all compounds studied, the HOMO–LUMO gap,
measured as the difference between the first reduction
and the first oxidation potentials, was in very good agree-
ment with the optical gap obtained from the energy of the
lowest energy band from the electronic spectra.
The structural features shown by the N-phenylquinolino-
[2,3,4-at]porphyrins4,namelythepresenceofatriarylam-
ine partly included in the aromaticity of the porphyrins,
prompted us to study the electrochemical properties of
this porphyrin series. It is well known that triarylamines
give stable radical cations (for example, the tris-4-bromo-
phenylamminium is commercially available). Therefore,
all of the derivatives of 4 were studied by cyclic voltam-
metry (CV) and by rotating disk electrode (RDV). The
results of the cyclic voltammetry experiments in dichlo-
romethane are summarized in Table 2. The RDV experi-
ments confirmed the CV data.
Due to the similar electronegativities of Cu and Ni
(1.90 and 1.91), the electrochemical behavior of Cu-4
and Ni-4 derivatives were almost identical. However, in
the case of Ni-2, a third oxidation was observed at a rather
high potential (E° = 1.15 V). The first two oxidations are
generally assigned to the oxidation of the macrocyclic
core [23]: from the neutral species Ni-2 to the radical-
cation and then to the dication; the nickel formally stays
in the Ni(II) state. The third oxidation might correspond
Compounds Ni-4 and Ni-5 are very similar from
a structural point of view and, as a consequence, their
electronic data are also analogous. However, the addi-
tion of the phenyl group on the external nitrogen trans-
forms the secondary amine in Ni-5 into a tertiary amine
in Ni-4. This tertiary amine might even be described
Fig. 2. Cyclic voltammetry of Ni-4
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A.M.V.M. PereIrA et al.
Fig. 3. Spectroelectrochemical studies of Ni-4. Changes in absorbance during oxidation of Ni-4 (left side) and evolution observed
during reduction of the generated species (right side)
as a triarylamine. During the previous electrochemical
studies of Ni-5, despite the nice electrochemical revers-
ibility observed in the cyclic voltammetry (at the usual
scan rates of 0.1 V/s), the compound underwent chemical
follow-up reactions during the spectroelectrochemical
studies, making this first oxidation chemically irrevers-
ible [24]; the radical cation reacted if the time scale was
longer than the CV recording time. Therefore, the first
oxidation of compound Ni-4 was studied carefully by
spectroelectrochemistry to see if the addition of the phe-
nyl group affected the electrochemical behavior.
In fact, the behavior was dramatically modified.
The presence of a tertiary amine gave a nicely revers-
ible first oxidation step not only on the cyclic voltam-
metry time scale, but also during the much longer time
period needed to record spectroelectrochemical data (see
Fig. 3). The chemical reversibility was also checked by
thin layer chromatography before and after the oxidation-
reduction procedure.
indication that the radical cation is localized on the exter-
nal nitrogen atom or very close to it.
CONCLUSION
In conclusion, we have shown that the nickel(II)
porphyrin complex Ni-5 can be used as an efficient precur-
sor, through a copper-mediated arylation, of the N-phenyl-
quinolino[2,3,4-at]porphyrins 4. The electronic properties,
photostability and the efficiency to generate singlet oxygen
suggest that some of these N-phenylquinolino[2,3,4-at]
porphyrins might have adequate features for photochemi-
cal applications. The reported porphyrins are functional-
ized at their periphery by a nitrogen atom that connects
the porphyrin core to a neighboring meso-phenyl group.
A detailed electrochemical study revealed that the stability
of the radical cation obtained after oxidation is strongly
dependant on the nature of the substituent present on this
external nitrogen atom.
Oxidation at a potential higher than that of the first oxi-
dation wave recorded for Ni-4 derivative gave very nice
spectral evolution over time. As expected for the genera-
tion of a radical cation, the intensity of the Soret band and
the Q-bands decreased. Three new bands at lower energy
appeared around 695, 750, and 895 nm. The radical-cat-
ion generated in this way was stable and the reduction
of this species led quantitatively to the starting material
Ni-4. The presence of an additional phenyl group on the
nitrogen atom (compared to Ni-5 compound) was clearly
the stabilizing factor. This observation is in good agree-
ment with the known stability of triarylamminiums. The
fact that the radical cation obtained from Ni-4 is stable
contrary to the one generated from Ni-5 might be a good
Acknowledgements
Continuous financial supports from the CNRS and
the Université de Strasbourg are acknowledged. Thanks
are due to Fundação para a Ciência e a Tecnologia (FCT,
Portugal) for funding the QOPNA Organic Chemistry
Research Unit. Ana M.V.M. Pereira is grateful to FCT for
her PhD grant (SFRH/BD/22691/2005). Authors thank
J-M Strub for recording HRMS spectra.
Dedicated to Prof. Karl M. Kadish on the occasion of
his 65th birthday: for his pioneering work in porphyrin
electrochemistry and his continuous involvement in the
SPP and JPP since the very beginning.
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Neves MGPMS and Tomé AC. J. Porphyrins Phtha-
locyanines 2009; 13: 408–414.
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