Bisporphyrin connected by pyrimidine: Synthesis and photo physical properties

Article abstract of DOI:10.1142/S1088424610002720

We report the synthesis of a series of zinc porphyrins conjugated with pyrimidine derivatives. V shaped porphyrin dimer with a pyrimidine central core exhibits a planar geometry according to DFT computational studies, presents an internal charge transfer upon excitation proved by typical solvatochromic behavior and moderate two-photon absorption properties. Such porphyrin conjugates can afford valuable advantages in applications of TPA materials such as in photodynamic therapy and imaging of biological entities.

Full text of DOI:10.1142/S1088424610002720

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2010; 14: 877–884
DOI: 10.1142/S1088424610002720
Published at http://www.worldscinet.com/jpp/
Bisporphyrin connected by pyrimidine: synthesis and
photophysical properties
Sylvain Achellea,b,c, Nicolas Saettela,b,c, Patrice Baldeckd,
Marie-Paule Teulade Fichoua,b,c and Philippe Maillard*a,b,c
a UMR 176 CNRS/Institut Curie, Institut Curie, Bât 110, Centre Universitaire, Univ. Paris-Sud, F-91405
Orsay, France
b Institut Curie, Section de Recherches, Centre Universitaire, Univ. Paris-Sud, F-91405 Orsay, France
c GDR CNRS 3049 “Médicaments Photoactivables - Photochimiothérapie (PHOTOMED)”,
d Laboratoire de Spectrométrie Physique, UMR 5588, Université Joseph Fourier/CNRS, 140 rue de la physique,
B.P. 87 38402 Saint Martin d’Hères cedex, France
Received 13 July 2010
Accepted 14 October 2010
ABSTRACT: We report the synthesis of a series of zinc porphyrins conjugated with pyrimidine
derivatives. V shaped porphyrin dimer with a pyrimidine central core exhibits a planar geometry
according to DFT computational studies, presents an internal charge transfer upon excitation proved
by typical solvatochromic behavior and moderate two-photon absorption properties. Such porphyrin
conjugates can afford valuable advantages in applications of TPA materials such as in photodynamic
therapy and imaging of biological entities.
KEYWORDS: porphyrin, pyrimidine, two photon absorption, cross coupling reactions.
absorbed by biological tissues. However, absorption
INTRODUCTION
is much lower in the optical window of biological tis-
Photodynamic therapy (PDT) is a promising light
sues in the near-infrared region between 700–1300 nm
activated treatment which is used in the clinic to destroy
[3]. Thus, greater treatment depths may be achieved
localized diseased tissues such as cancers [1]. When
by exciting the photosensitizers via simultaneous two-
exposed to light, a photosensitive molecule called pho-
photon absorption (TPA) with near infrared light. Por-
tosensitizer (Ps) transfers energy from its first triplet
phyrin compounds have strong one-photon absorption
excited state to ground-state triplet oxygen molecule
between 400 and 500 nm (Soret Band) corresponding to
generating highly reactive oxygen species (ROS) as sin-
the combined energy of two photons in the wavelength
glet oxygen, inducing oxidative damages to the cell and
range from 800 to 1000 nm, that matches to the optical
causing localized cell death. Major advantage of PDT in
window. Monomeric porphyrins without donor/acceptor
comparison with other treatments such as chemotherapy
groups have only small TPA cross section of less than a
is that, in the absence of light, the Ps is benign. The
few tens of GM where 1 GM = 10-50 cm4.s.molecule-1 [4].
majority of photosensitizers are cyclic tetrapyrroles or
However conjugative extensions via meso-meso conju-
porphyrinoids because of their long triplet lifetime [2].
gated bridges have led to dramatic improvements in the
These Ps have one-photon absorption peaks in the visible
TPA cross section values for this class of molecules
wavelength range (400–700 nm) but one concern is the
[5]. In order to obtain conjugated porphyrin oligomers,
low penetration depth of visible light which is strongly
monomers should be linked with bridges that do not
twist out the plane with the porphyrin due to steric hin-
drance. Alkynyl bridges are then one of the most effec-
tive way of making connections to the meso-position
of a porphyrin. Butadiyne [6], diethynylbenzene [7],
*Correspondence to: Philippe Maillard, email: philippe.
maillard@curie.u-psud.fr, tel: +33 (0)1-69-86-31-71, fax: +33
(0)1 69-07-53-27
Copyright © 2010 World Scientific Publishing Company

878
S. AChelle et al.
diethynylthiophene [8], diethynylanthracene [9], diethy-
nyltetrathiafulvalene [10], diethynylsquaraine [11] and
triethynylphenylamine [12] π-conjugated cores have
been described in the literature.
N
N
N
N
During the past decade, pyrimidine and its deriva-
tives have been extensively studied as electron acceptor
in conjugated structures. When combined with electron
donor parts, interesting D-A molecules are obtained and
fluorescence with internal charge transfer excited state is
observed [13]. Oligomers that contain pyrimidine rings
have been used as n-type semi-conductor [14], compo-
nents of electroluminescent diodes [15], pH and polarity
sensors [16] and two photon absorption chromophores
[17]. Recently dendrimers [18] and supramolecular [19]
receptors combining porphyrin and pyrimidine units have
been described by Dehaen.
N
N
Zn
N
Zn
N
N
N
1
Fig. 1. Chemical structure of bisporphyrin conjugate 1
RESULTS AND DISCUSSION
The one-electron reduction of pyrimidine gives its
anion radical with a reduction potential of ca. 2.63 V vs.
Ag/AgCl [20] whereas the one-electron oxidation and
reduction potentials of tetraphenylporphyrins are around
0.8 and 1 V and -1.11 to -1.33 V respectively [21]. This
suggests that porphyrin could become a donor unit when
conjugated with pyrimidine to afford interesting D-A
molecules with potential TPA properties.
Synthesis
Compound 1 could be obtained by cross coupling
reaction of 5-ethynyl-10,15,20-triarylporphyrin derived
from protected trimethylsilylethynyl porphyrin 6 with
4,6-dihalogenopyrimidine under Heck or Sonogashira
conditions.
Porphyrin monomer 6 was prepared, in four steps,
from porphyrin 2 [22] (Scheme 1). The first step con-
sists in the addition of phenyllithium in THF [23]. Mono-
bromination with NBS and metalation with zinc acetate
The aim of this paper is to describe synthesis and photo-
physical properties including non linear absorption prop-
erties of bisporphyrin connected by pyrimidine (Fig. 1).
N
N
NH
N
N
N
N
NH
N
N
(i)
(ii)
Br
M
HN
HN
2
3
4 M = 2H
5 M = Zn
(iii)
(iv)
N
N
N
N
SiMe3
Zn
6
Scheme 1. (i) C6H5Li, THF, rt, 2 h, then O2, 65%; (ii) NBS, pyridine, CHCl3, 0 °C, 15 min, 97%; (iii) Zn(OAc)2, CHCl3/MeOH, ∆,
5 min, 99%; (iv) TMSA, CuI, Pd(PPh3)2Cl2, THF/Et3N, -196 °C → rt, 15 h, 89%
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 878–884

BISPOrPhyrIn COnneCteD By PyrImIDIne: SyntheSIS AnD PhOtOPhySICAl PrOPertIeS
879
N
N
N
N
(i)
6
Zn
7
(iii)
(ii)
SMe
N
N
N
N
N
N
N
N
N
N
1
N
Zn
N
I
+
Zn
8
9
Scheme 2. (i) TBAF, THF/CH2Cl2, rt, 30 min, non-isolated; (ii) 4-iodo-2-thiomethylpyrimidine, CuI, Pd(PPh3)2Cl2, THF/Et3N, rt,
15 h, 46%; (iii) 4,6-diiodopyrimidine, CuI, Pd(PPh3)2Cl2, THF/Et3N, rt, 15 h, 9: 33%, 1: 40%
led quantitatively to zinc porphyrin 5. Sonogashira cross
coupling reaction with ethynyltrimethylsilane in the pres-
ence of CuI and Pd(PPh3)2Cl2, leads to porphyrin mono-
mer 6 in good yield.
Calculated geometric properties
To explore geometrical features of bisporphyrin
connected by pyrimidine, DFT calculation at the B3LYP/
321++G* level of theory was performed [25]. Phenyl
groups and zinc atoms were omitted for simplification.
The optimized geometry reveals that the two porphyrin
macrocycles in dimer 1 adopts a completely planar struc-
ture as shown on Fig. 2, indicating a good conjugation
between the porphyrin rings and the pyrimidine central
core.
Synthesis of ethynylporphyrin pyrimidines starts with
the deprotection of trimethylsilyl group of compound 6
with TBAF to lead quantitatively to compound 7 which
was not isolated due to its instability and was immedi-
ately engaged in the following reaction. Sonogashira
cross coupling was revealed to be more efficient than
Heck cross coupling reaction, generally used to link
ethynylporphyrins to halogenoaryl [24]: compounds 1, 8
and 9 have been obtained in moderate rate starting from
4-iodo-2-thiomethylpyrimidine and 4,6-diiodopyrimi-
dine (Scheme 2). It should be noted that even when using
4 equivalents of ethynylporphyrin with 4,6-diiodopyrim-
idine, a mixture of monocoupled product 9 (33%) and
dicoupled product 1 (40%) as well as the butadiyne core
porphyrin dimer was obtained. Yield of product 1 was
not upgraded by increasing the temperature. Compound
9 can be recycled by reaction with 7 to give product 1. All
porphyrin compounds were fully characterized. Assign-
ments of the NMR resonance to individual protons are
based on integration and selective homonuclear correla-
tion (COSY). Heteronuclear multiple coherence (HMQC,
HMBC) spectra were also obtained for all compounds
and allow assignments of the NMR resonance to carbon
atoms. Data of MALDI-TOF and elemental analyses
for all compounds are consistent with their molecular
formula.
Absorption and fluorescence properties
Figure 3 shows the UV-vis absorption spectra of com-
pounds 1, 6, 8 and 9 in dichloromethane. The Soret bands
of ethynylpyrimidine porphyrins 1, 8 and 9 (444–445 nm)
are red shifted of about 15 nm in comparison with por-
phyrin building block 6 (430 nm). The less energetic
Q-band denoted Q(0,0) is also red shifted (from 606
nm for compound 6 to 619–625 nm for compounds 1, 8
Fig. 2. The optimized geometry of compound 1 (phenyl rings
and zinc atoms have been omitted for simplification) by DFT
calculation
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 879–884

880
S. AChelle et al.
Fig. 3. Normalized absorption spectra of compounds 1, 6, 8 and 9 in dichloromethane, c = 5 × 10-6–10-5 M
and 9). On the contrary, the first Q-band [Q(1,0)] between
564–568 nm was not significantly modified by coupling
with pyrimidine. When the spectrum of bisporphyrin 1 is
compared to these of porphyrins 8 and 9, no important
differences concerning the absorption band position are
observed, however their relative intensity is modified: the
Soret band of dimer 1 is remarkably broadened and lower
relative to that of monomer 8 and 9 whereas the Q-bands
are two times more intense in case of dimer. This is in
agreement with the literature concerning conjugated
porphyrin oligomers [26]. As shown on absorption
spectra, the ground state absorption of dimer 1 remark-
ably differs from that of monomers 8 and 9, this indi-
cating an electronic coupling between the porphyrin
chromophores which is consistent with calculated geo-
metrical features of 1.
Emission spectra of compounds 1, 6, 8 and 9 in
dichloromethane are presented in Fig. 4 and photophysi-
cal parameters are summarized in Table 1. As expected in
view of the literature [27], porphyrins derivatives exhibit
two emission bands Q(0,0) and Q(0,1) respectively at
645–648 and 692–698 nm by excitation at 440 nm for
the porphyrins conjugated to pyrimidine, these band
are shifted to lower energy than those of building block
6 (630 nm and 679 nm). As described in the literature
for porphyrins derivatives the relative intensity of these
two bands strongly depend on the excitation wavelength
[27b]. A fluorosolvatochromic study has been carried
Fig. 4. Normalized emission of compounds 1, 6, 8 and 9 in dichloromethane, c = 5 × 10-7–10-6 M
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 880–884

BISPOrPhyrIn COnneCteD By PyrImIDIne: SyntheSIS AnD PhOtOPhySICAl PrOPertIeS
881
Table 1. Photophysical parameters of porphyrins 1, 6, 8 and 9 in dichloromethane. λmax(abs) is the
absorption peaks wavelength in nm, ε is extinction coefficient in L.mmol-1.cm-1, λmax(em) the absorp-
tion peaks wavelength in nm (excitation at absorption maximum), ΦF is the fluorescencequantum yield
in ethanol vs. Rhodamine 101 (1.00) [32]
Compound
1
6
8
9
λ
max(abs)
444, 565, 622
549, 45, 76
648, 702
0.11
430, 564, 606
543, 17, 12
630, 679
0.14
440, 568, 619
610, 19.7, 28.2
643, 693
444, 568, 625
660, 24, 43
645, 692
0.12
ε
λ
max(em)
ΦF
0.18
Fig. 5. Normalized emission of compound 1 in various solvent. c = 10-6 M
out on compounds 1 and 6. For compound 1, a batho-
chromic shift of highest energy emission band can be
observed with increasing solvent polarity estimated by
solvent orientation polarizability [28] (Fig. 5). In con-
trast the absorption is not significantly shifted. The emis-
sion spectrum shape in methanol is modified relative to
other solvents probably due to aggregation of compound
1 in this solvent at working concentration. This solva-
tochromic behavior, which results from the stabiliza-
tion of the highly polar emitting state by polar solvents,
is typical for compounds presenting an internal charge
transfer upon excitation and has been fully documented
with donor-acceptor fluorophores [29]. On the contrary,
no significant fluorosolvatochromy is observed with
compound 5 except with solvents such as pyridine that
are able to complex zinc cations in porphyrin rings and
Fig. 6. TPA spectra of compound 1 in DCM. c = 10-6 M
lead to a bathochromic shift (λemDCM = 630 nm, λemPyridine
=
(δmax = 45 GM) corresponding to two photon excitation of
Q(0,0)absorptionbandwhereasforfluorescenceemission
collected at 702 nm [Q(0,1) band], the highest recorded
cross section is observed at 930 nm (δmax = 120 GM)
corresponding to two photon excitation of Q(1,0) absorp-
tion band. Similar TPA bands have been previously
obtained for porphyrin dimers [30]. These results indi-
cates that compound 1 exhibits better two photon cross
section than the corresponding monomer (about 20 GM)
637 nm).
Two photon properties
TPA spectrum of compound 1 has been determined by
detecting the upconverted fluorescence following excita-
tion between 790–950 nm. As shown in Fig. 6, for fluo-
rescence emission collected at 648 nm [Q(0,0) band], the
highest recorded cross section is observed around 790 nm
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 881–884

882
S. AChelle et al.
[26] and validate the oligomeric design [5]. However
these values remain lower than other porphyrin dimers
linked with a butadiyne and an ethynyl bridge (more than
5000 GM) [26]. This may be explained by a lower conju-
gation between the porphyrin rings via meta-pyrimidine
moiety leading to a lower resonance of excitation light
with the Q-bands.
Synthesis
5,10,15-triphenyl-20-trimethylsilanylethynyl por-
phyrinato Zn(II) (6) [32]. A flask containing 5-bromo-
porphyrin 5 (800 mg, 1.17 mmol), CuI (22 mg, 0.12
mmol) and Pd(PPh3)2Cl2 (82 mg, 0.12 mmol) was purged
with N2, and then charged with anhydrous THF (40 mL)
and dry Et3N (7.2 mL).After this solution was frozen with
liquid nitrogen, trimethylsilylacetylene (2.34 mL, 16.4
mmol) was added and the mixture was then degassed.
The mixture was stirred for 12 h at room temperature,
quenched with water and evaporated to remove organic
solvents. Organic compounds were extracted with DCM,
the organic layer was dried over anhydrous Na2SO4, fil-
tered and evaporated to dryness under reduced pressure.
The residue was separated over a silica gel column with
heptane/DCM (1/1, v/v) to give 6 (730 mg, 89%) as a
purple solid. UV-vis (CH2Cl2): λmax, nm (ε, L.mmol-1.
cm-1) 430 (543), 564 (17), 606 (12). 1H NMR (300 MHz,
CDCl3, Me4Si): δH, ppm 9.76 (d, 2H, J = 4.8 Hz, H-2,
18), 8.98 (d, 2H, J = 4.8 Hz, H-3, 17), 8.87 (s, 4H, H-7,
13/8, 12), 8.20–8.16 (m, 12H, H-Ph), 7.78–7.73 (m,
18H, H-Ph), 0.61 [s, 9H, Si(CH3)3]. 13C NMR (75 MHz,
CDCl3, Me4Si): δC, ppm 152.6–149.9 (C-1, 19/4, 16/6,
14/9, 11), 142.6 (C-1Ph), 142.5 (C-1Ph), 134.4 (C-Ph),
134.3 (C-Ph), 132.9–131.0 (C-2, 3, 7, 8, 12, 13, 17,
18), 127.6 (C-Ph), 126.6 (C-Ph), 126.5 (C-Ph), 122.9
(C10), 121.9 (C-5/15), 107.6 (C-20), 101.3 (C-alkyne),
99.7 (C-alkyne). Anal. calcd. for C43H32N4SiZn + H2O
(716.23): C 72.11, H 4.78, N 7.82. Found C 72.21, H
4.93, N 7.56.
5,10,15-triphenyl-20-ethynyl porphyrinato Zn(II)
(7). Tetrabutylammonium fluoride (TBAF) in solution
in THF (1 M, 0.744 mL) was added to a solution of 6
(200 mg, 0.286 mmol) dissolved in DCM (12 mL). The
reaction was stirred at room temperature for 15 min, fol-
lowed by addition of anhydrous calcium chloride (2 g).
The mixture was stirred for 10 min, filtered into a flask
and the solvent evaporated.
General procedure for Sonogashira cross-coupling
reaction. Porphyrin 7 (0.286 mmol) was combined with
iodopyrimidine (0.125 mmol), CuI (0.029 mmol) and
Pd(PPh3)2Cl2 (0.029 mmol) in anhydrous THF (10 mL)
and Et3N (10 mL) under argon. The reaction mixture was
stirred at room temperature overnight then poured from
the reaction vessel into a separatory funnel containing
50 mL of H2O and 50 mL of DCM. The layers were sepa-
rated, the aqueous layer was extracted with DCM (3 ×
25 mL) and the combined organic layers were washed
with water and dried over sodium sulfate, filtered and
evaporated under reduced pressure. Crude product was
purified by chromatography over preparative TLC (silica,
AcOEt/n-heptane (3/7, v/v)).
EXPERIMENTAL
Materials
All solvents (reagent grade) and the starting materi-
als were acquired from Sigma-Aldrich and were used
without purification. Methylene chloride (DCM) was
distilled from calcium hydride and kept over 4 Å sieves.
Tetrahydrofuran (THF) was distilled from sodium/ben-
zophenone. Et3N was dried and kept over potassium
hydroxide. Column chromatography was performed with
the indicated solvents using E. Merck silica gel 60 (par-
ticle size 0.035–0.070 mm). Macherey-Nagel precoated
plates (SIL G-200, 2 mm) were used for preparative
thin-layer chromatography. Yields refer to chromato-
1
graphically and spectroscopically pure compounds. H
and 13C NMR spectra were recorded on a Bruker AC-300
spectrometer at ambient temperature using an internal
deuterium lock. Chemical shift values are given in ppm
relative to tetramethyl silane (TMS). Acidic impurities
in CDCl3 were removed by treatment with anhydrous
K2CO3. Quantitative UV-vis spectra were recorded
with a UVIKON xm SECOMAM spectrometer (molar
extinction coefficient values are given in L.mmol-1.
cm-1). Fluorescence spectra were recorded using Spex
FluoroMax-3 Jobin-Yvon Horiba apparatus. Micro-
analysis were obtained from ICSN-CNRS Elemental
Analysis Center at Gif-sur-Yvette, France. The MALDI-
TOF mass spectra were performed with MALDI-TOF
Voyager Spec equipped with a N2 Laser emitting at
337 nm. The TPA cross-section in the range 750–950 nm
were obtained by up-conversion fluorescence using a
mode locked Ti:sapphire femtosecond laser (Tsunami
Spectra-Physics) with pulse duration 100 fs and at a rep-
etition rate of 82 MHz. The measurements were done at
room temperature in DCM and at concentration of 5 ×
10-6 M–10-5 M. The excitation beam (5 mm diameter) is
focalized with a lens (focal length 10 cm) at the middle
of the fluorescence cell (10 mm). The fluorescence, col-
lected at 90° to the excitation beam, was focused into
an optical fiber (diameter 600µm) connected to an
Ocean Optics S2000 spectrometer. The incident beam
intensity was adjusted to 50 mW in order to ensure an
intensity-squared dependence of the fluorescence over
the whole range. The detector integration time was fixed
to 1s. Comparison of the spectra was performed with
the published Fluorescein and Rhodamine B two-photon
absorption spectra [31].
Bis[5-ethynyl-(10,15,20-triphenyl)porphyrinato
Zn(II)]-4′,6′-pyrimidine 1. Dark green solid (66 mg,
40%). UV-vis (CH2Cl2): λmax, nm (ε, L.mmol-1.cm-1) 444
1
(549), 565 (45), 622 (76). H NMR (300 MHz, Pyrd5,
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 882–884

BISPOrPhyrIn COnneCteD By PyrImIDIne: SyntheSIS AnD PhOtOPhySICAl PrOPertIeS
883
Me4Si): δH, ppm 10.33 (d, 4H, J = 4.5 Hz, H-2, 18), 9.88
(http://www.retinostop.org). Sylvain Achelle also thanks
the fondation Pierre-Gilles de Gennes for a postdoctoral
fellowship.
(s, 1H, H-2pyrim), 9.23 (d, 4H, J = 4.5 Hz, H-3, 17), 9.05
(d, 4H, J = 4.5 Hz, H-7, 13/8, 12), 9.02 (d, 4H, J = 4.5 Hz,
H-7, 13/8, 12), 8.98 (s, 1H, H-5pyrim), 8.36–8.34 (m, 12H,
H-Ph), 7.81–7.76 (m, 18H, H-Ph). MS (MALDI-TOF):
m/z 1325.25 (C84H49N10Zn2, [M + H]+, requires 1325.27).
Anal. calcd. for C84H48N10Zn2 + 11 H2O: C 66.10, H 4.62,
N 9.18. Found C, 66.06 H, 4.53 N, 8.95.
REFERENCES
1. a) Dougherty TJ, Gomer CJ, Henderson BW, Jori
G, Kessel D, Korbelik M, Moan J and Peng Q. J.
Nat. Canc. Inst. 1998; 90: 889–905. b) Chemical
Aspects of Photodynamic Therapy, Bonnet R. (Ed.)
Gordon and Breach Science Publishers: Amster-
dam, 2000. c) MacDonald IJ and Dougherty TJ. J.
Porphyrins Phthalocyanines 2001; 5: 105–129. d)
Dolmans DEJGJ, Fukumura D and Jain RK. Nat.
Rev. 2003; 3: 380–386. e) Robertson CA, Hawkins
Evans D and Abrahamse H. J. Photochem. Photo-
biol., B 2009; 96: 1–8.
2. Bonnett R. Chem. Soc. Rev. 1995; 24: 19–33.
3. a) Electrooptics Handbook, Waynant RW and Edi-
ger MN. (Eds.) McGraw-Hill: New York, 1993;
Chapter 24. b) Tromberg BJ, Shah N, Lanning R,
Cerussi A, Espinoza J, Pham T, Svaasand L and
Butler J. Neoplasia 2000; 2: 26.
[5-ethynyl-(10,15,20-triphenyl)porphyrinato
Zn(II)]-2′-(methylthio)pyrimidine 8. Dark green solid
(43 mg, 46%). UV-vis (CH2Cl2): λmax, nm (ε, L.mmol-1.
1
cm-1) 440 (610), 568 (19.7), 619 (28.2). H NMR (300
MHz, CDCl3, Me4Si): δH, ppm 9.76 (d, 2H, J = 4.8 Hz,
H-2, 18), 9.00 (d, 2H, J = 4.8 Hz, H-3, 17), 8.86 (d, 2H,
J = 4.8 Hz, H-7, 13/8, 12), 8.83 (d, 2H, J = 4.8 Hz, H-7,
13/8, 12), 8.46 (d, 1H, J = 5 Hz, H-6pyrim), 8.20–8.15 (m,
6H, H-Ph), 7.78–7.73 (m, 9H, H-Ph), 7.47 (d, 1H, J =
5 Hz, H-5pyrim), 2.67 (s, 3H, SMe). MS (MALDI-TOF):
m/z 748.14 (calcd. for [M]+ 748.14). Anal. calcd. for
C45H28N6SZn + 8 H2O: C 60.43, H 4.96, N 9.40, S 3.59.
Found C, 60.81 H, 5.25 N, 9.51, S 3.43.
[5-ethynyl-(10,15,20-triphenyl)porphyrinato
Zn(II)]-6′-(iodo)pyrimidine 9. Dark green solid (34 mg,
33%). UV-vis (CH2Cl2): λmax, nm (ε, L.mmol-1.cm-1) 444
4. a) Goyan RL and Cramb DT. Photochem. Photobiol.
2000; 72: 821–827. b) Dichtel WR, Serin JM, Edder
C, Frechet JM, Matuszewski M, Tan LS, Ohulchan-
skyy TY and Prassad PN. J. Am. Chem. Soc. 2004;
126: 5380–5381.
1
(660), 568 (24), 625 (43). H NMR (300 MHz, CDCl3,
Me4Si): δH, ppm 9.32 (d, 2H, J = 4.8 Hz, H-2, 18), 8.94
(d, 2H, J = 4.8 Hz, H-3, 17), 8.85 (d, 2H, J = 4.8 Hz,
H-7, 13/8, 12), 8.81 (d, 2H, J = 4.8 Hz, H-7, 13/8, 12),
8.20–8.18 (m, 7H, H-Ph + H-2pyrim), 7.90 (s, 1H, H-5pyrim),
7.80–7.76 (m, 9H, H-Ph). 13C NMR (75 MHz, CDCl3,
Me4Si): δC, ppm 170.0 (C-2pyrim), 154.0 (C-4pyrim), 153.0–
149.6 (C-1, 19/4, 16/6, 14/9, 11), 142.73 (C-1Ph), 142.67
(C-1Ph), 134.4 (C-Ph), 134.3 (C-Ph), 131.6–131.1, (C-2,
3, 7, 8, 12, 13, 17, 18), 128.2 (C-Ph), 128.1 (C-Ph), 127.5
(C-5pyrim), 126.5 (C-Ph), 126.4 (C-Ph), 122.6 (C-5/15)
121.9 (C-10), 106.4 (C-20), 103.4 (C-alkyne), 97.1
(C-alkyne). MS (MALDI-TOF): m/z 828.05 (calcd. for
[M]+ 828.06).
5. a) Karotki A, Drobizhev M, Dzenis Y, Taylor PN,
Anderson HL and Rebane A. Phys. Chem. Chem.
Phys. 2004; 6: 7–10. b) Frampton MJ, Akdas H,
Cowley AR, Rogers JE, Slagle JE, Fleitz PA, Dro-
bizhev M, Rebane A and Anderson HL. Org. Lett.
2005; 7: 5365–5368. c) He GS, Tan LS, Zheng Q
and Prasad PN. Chem. Rev. 2008; 108: 1245–1330.
6. a) Arnold DP, Johnson AW and Mahendran M.
J. Chem. Soc. Perkin Trans. 1 1978; 366–370. b)
Arnold DP and James DA. J. Org. Chem. 1997;
62: 3460–3469. c) Anderson HL. Chem. Commun.
1999; 2323–2330. d) Balaz M, Collins HA, Dahlst-
edt E and Anderson HL. Org. Biomol. Chem. 2009;
7: 874–888. e) Kuimova MK, Collins HA, Balaz M,
Dahlstedt E, Levitt JA, Sergent N, Suhling K, Drobi-
zhev M, Makarov NS, Rebane A, Anderson HL and
Phillips D. Org. Biomol. Chem. 2009; 7: 889–904.
f) Collins HA, Khurana M, Moriyama EH, Mari-
ampillai A, Dahlstedt E, Balaz M, Kuimova MK,
Drobizhev M, Yang VXD, Phillips D, Rebane A,
Wilson BC and Anderson HL. Nat. Photonics 2008;
2: 420–424.
CONCLUSION
In this contribution, we have successfully synthesized
a V-shaped bisporphyrin conjugate using a meta-difunc-
tionalized pyrimidine core and two meso-ethynylporphy-
rin arms. Computational and photophysical studies show
that this structure is a promising D-π-A-π-D fluorophore.
Such porphyrin conjugates can afford valuable advan-
tages in applications of TPA materials such as in photo-
dynamic therapy and imaging of biological entities.
7. a) Arnold DP and Nitschinsk LJ. Tetrahedron Lett.
1993; 34: 693–696. b) Arnold DP and James DA. J.
Org. Chem. 1997; 62: 3460–3469.
8. Arnold DP, James DA, Kennard CHL and Smith G.
J. Chem. Soc. Chem. Commun. 1994; 2131–2132.
9. Taylor PN, Wylie AP, Huuskonen J and Anderson
HL. Angew. Chem. Int. Ed. 1998; 37: 986–989.
Acknowledgements
We thank Mr. Jean Bernard for TPA measurements,
Mr Vincent Guérineau for MALDI-TOF analysis and the
center of computing services of the Paris-Sud IT depart-
ment. This work has been supported by INCa (2009–1-
RT-08-IC-1) and the French association “Rétinostop”
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 883–884

884
S. AChelle et al.
10. Ogawa K and Nagatsuka Y. J. Porphyrins Phthalo-
cyanines 2009; 13: 114–121.
b) Maes W, Amabilino DB and Dehaen W. Tetrahe-
dron 2003; 59: 3937–3943. c) Maes W and Dehaen
W. Eur. J. Org. Chem. 2009; 4719–4752.
11. Odom SA, Webster S, Padilha LA, Peceli D, Hu
H, Nootz G, Chung SJ, Ohira S, Matichak JD,
Przhonska OV, Kachkovski AD, Barlow S, Bré-
das JL, Anderson HL, Hagan DJ, Van Stryland
EW and Marder SR. J. Am. Chem. Soc. 2009; 131:
7510–7511.
19. Van Rossom W, Kundrát O, Ngo TH, Lhotk P,
Dehaen W and Maes W. Tetrahedron Lett. 2010; 51:
2423–2426.
20. a) Elving PJ and O’Reilly JE. J. Am. Chem. Soc.
1971; 93: 1871–1979. b) O’Reilly JE and Elving PJ.
J. Electroanal. Chem. 1977; 75: 507–522.
21. a) Hodge JA, Hill MG and Gray HB. Inorg. Chem.
1995; 34: 809–812. b) Ravikanth M, Reddy D,
Misra A and Chandrashekar TK. J. Chem. Soc.
Dalton Trans. 1993; 1137–1141.
22. Varamo M, Loock B, Maillard Ph and Grierson DS.
Org. Lett. 2007; 9: 4689–4692.
23. a) Kalicsh WW and Senge MO. Angew. Chem. Int.
Ed. 1998; 37: 1107–1109. b) Senge MO and Feng
X. Tetrahedron Lett. 1999; 40: 4165–4168.
24. Raymond JE, Bhaskar A, Goodson III T, Makiuchi
N, Ogawa K and KobukeY. J. Am. Chem. Soc. 2008;
130: 17212–17213.
25. Jaguar, version 7.6, Schrodinger, LLC, New York,
NY 2009.
26. Drobizhev M, Stepanenko Y, Dzenis Y, Karotki A,
Rebane A, Taylor PN and Anderson HL. J. Phys.
Chem. B 2005; 109: 7223–7236.
27. a)Pérez-Morales M, de Miguel G, Bolink HJ,
Martín-Romero MT and Camacho L. J. Mater.
Chem. 2009; 19: 4255–4260. b) Suriyanarayanan P
and Krishnan V. Photochem. Photobiol. 1983; 38:
533–536.
28. Myśliwa-Kurdziel B, Solymosi K, Kruk J, Böddi B
and Strzalka K. Eur. Biophys. J. 2008; 37: 1185–1193.
29. a) Katan C, Terenziani F, Mongin O, Werts MHV,
Porres L, Pons T, Mertz J, Tretiak S and Blanchard-
Desce M. J. Phys. Chem. A 2005; 109: 3024–3037.
b) Lartia R,Allain C, Bordeau G, Schmidt F, Fiorini-
Debuischert C, Charra F and Teulade-Fichou MP. J.
Org. Chem. 2008; 73: 1732–1744.
30. Odom SA, Kelley RF, Ohira S, Ensley TR, Huang C,
Padilha LA, Webster S, Coropceanu V, Barlow S,
Hagan DJ, Van Stryland EW, Brédas JL, Ander-
son HL, Wasielewski MR and Marder SR. J. Phys.
Chem. A 2009; 113: 10826–10832.
31. Makarov NS, Drobizhev M and Rebane A. Proc.
SPIE 2008; 6891: 689105.
32. Fathalla M and Jayawickramarajah J. Eur. J. Org.
Chem. 2009; 6095–6099.
12. Seo JW, Jang SY, Kim D and Kim HJ. Tetrahedron
2008; 64: 2733–2739.
13. a) Pascal L, Vanden Eynde JJ, Van Haverbeke Y,
Dubois P, Michel A, Rant U, Zojer E, Leising G,
Van Dorn LO, Gruhn NE, Cornil J and Brédas JL.
J. Phys. Chem. B 2002; 106: 6442–6450. b) Itami
K, Yamazaki D and Yoshida J. J. Am. Chem. Soc.
2004; 126: 15396–15397. c) Achelle S, Ramon-
denc Y, Dupas G and Plé N. Tetrahedron 2008; 64:
2783–2791. d) Achelle S, Plé N, Kreher D, Attias
AJ, Arfaoui I and Charra F. Tetrahedron Lett. 2009;
50: 7055–7058.
14. Kambara T, Kushida T, Saito N, Kuwayiama I,
Kubuta K and Yamamoto T. Chem. Lett. 1992; 583.
15. a) Wang C, Jung GY, Batsanov AS, Bryce MR and
Petty MC. J. Mater. Chem. 2002; 12: 173–180.
b) Wong KT, Hung TS, Lin Y, Wu CC, Lee GH,
Peng SM, Chou CH and Su YO. Org. Lett. 2002;
4: 513–516.
16. a) Achelle S, Ramondenc Y, Marsais F and Plé N.
Eur. J. Org. Chem. 2008; 3129–3140. b) Achelle
S, Nouira I, Pfaffinger B, Ramondenc Y, Plé N and
Rodríguez-López J. J. Org. Chem. 2009; 74: 3711–
3717. c) Bagley MC, Lin Z and Pope SJA. Tetrahe-
dron Lett. 2009; 50: 6818–6822.
17. a) Liu Z, Chen T, Liu B, Huang Z-L, Huang T,
Li S, Xu Y and Qin J. J. Mater. Chem. 2007; 17:
4685–4689. b) Liu B, Hu XL, Liu J, Zhao YD and
Huang ZL. Tetrahedron Lett. 2007; 48: 5958–5962.
c) Liu Z, Shao P, Huang Z, Liu B, Chen T and Qin
J. Chem. Commun. 2008; 2260–2262. d) Li L, Tian
YP, Yang JX, Sun PP, Wu JY, Zhou HP, Zhang SY,
Jin BK, Xing XJ, Wang CK, Li M, Cheng GH, Tang
HH, Huang WH, Tao XT and Jiang MH. Chem.
Asian J. 2009; 4: 668. e) Akdas-Kilig H, Roisnel T,
Ledoux I and Le Bozec H. New J. Chem. 2009; 33:
1470–1473.
18. a) Maes W, Vanderhaeghen J, Smetts S, Asokan
CV, Van Renterghem LM, Du Prez FE, Smet M and
Dehaen W. J. Org. Chem. 2006; 71: 2987–2994.
Copyright © 2010 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2010; 14: 884–884