Synthesis of new crosslinkable co-polymers containing a push-pull zinc porphyrin for non-linear optical applications

Article abstract of DOI:10.1016/j.tet.2005.07.094

In this paper, the synthesis of a crosslinkable co-polymer containing new push-pull arylethynyl zinc porphyrins is described. The synthesis of porphyrin chromophores, analogous to Therien's porphyrin (J. Am. Chem. Soc. 1996, 118, 1497-1503) functionalized

Full text of DOI:10.1016/j.tet.2005.07.094

Tetrahedron 61 (2005) 10113–10121
Synthesis of new crosslinkable co-polymers containing a push–pull
zinc porphyrin for non-linear optical applications
a
Cyrille Monnereau, Errol Blart, Veronique Montembault, Laurent Fontaine
a
b
b
´
and Fabrice Odobela,
*
a
` ´
Laboratoire de Synthese Organique, UMR CNRS 6513 & FR CNRS 2465, Faculte des Sciences et des Techniques de Nantes, BP 92208,
`
2, rue de la Houssiniere, 44322 Nantes Cedex 03, France
´
b
´ ´
Unite de Chimie Organique Moleculaire et Macromoleculaire, UCO2M-UMR CNRS 6011, Avenue O. Messiaen,
72085 Le Mans cedex 9, France
Received 10 May 2005; revised 27 July 2005; accepted 29 July 2005
Available online 6 September 2005
Abstract—In this paper, the synthesis of a crosslinkable co-polymer containing new push–pull arylethynyl zinc porphyrins is described. The
synthesis of porphyrin chromophores, analogous to Therien’s porphyrin (J. Am. Chem. Soc. 1996, 118, 1497–1503) functionalized with a
methacrylic polymerizable group and a carboxylic acid crosslinking group was achieved with a new synthetic procedure leading to a higher
overall yield compared to what was previously reported in the literature for similar and simpler structures. Radical copolymerization of the
porphyrin chromophore with glycidyl methacrylate has then been carried out with success. This work opens a perspective on the possibility to
integrate porphyrinic chromophore with high first-order molecular quadratic hyperpolarizability coefficient in opto-electronic devices.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
Increasing stability of the nonlinear response consists in
limiting the relaxation of the field-induced orientation of the
chromophores in the matrix. This is generally achieved by
two strategies. The first one consists in grafting the
chromophore into a polymeric matrix of high glass-
transition temperature. Many examples using polyimide
matrices have proved the efficiency of such approach.1,2,15
Its main drawback stems from the need to perform the
poling process at high temperature, which can cause partial
thermal decomposition of the chromophores. A less severe
approach consists in locking the chromophore orientation
after the poling process by a crosslinking reaction. Some
recent examples using different crosslinkable strategies
have been reported and have fully demonstrated the validity
of such an approach.1,2,16–20 More particularly, a cross-
linking reaction based on the opening of an epoxy group by
a carboxylic acid carried by the chromophore proved to be
quite efficient to lock the chromophores orientation after
poling.21–23
The increasing need of optoelectronic devices for tele-
communications, optical switching and information storage
has led to a tremendous research activity in the area of non-
linear optic (NLO) materials.1,2 Amongst the wide range
of NLO chromophores investigated in the last 15 years,
organometallic and coordination compounds probably
appear as the most promising.3–6 Therien and co-workers
have reported a push–pull arylethynyl porphyrin chromo-
phore with exceptional first-order molecular quadratic
hyperpolarizability coefficient (b).7–9 The presence of zinc
inside the porphyrin core appears to be essential to
guarantee high b value, as demonstrated by other studies
on push–pull nickel or copper porphyrins.10–12 However, to
consider practical applications, the active NLO chromo-
phores must be inserted in a matrix to be subsequently cast
into films. Polymeric materials are, by far, the most
convenient matrix used to host NLO chromophores for the
development of materials exhibiting macroscopic electro-
optic properties.1,2 Besides this, long-term stability of the
macroscopic electro-optic activity of the material is of a
high importance for its future commercial development.13,14
In spite of its numerous qualities (large b value and high
thermal stability), Therien’s chromophore has never been,
up to now, covalently integrated into a polymeric material.
Herein, we report on a new synthetic strategy to prepare
gram-scale of new push–pull porphyrins and their success-
ful copolymerization with glycidyl methacrylate (GMA).
The introduction of a methacrylate group and a carboxylic
Keywords: Porphyrin; Push–pull; Polymer; Non-linear optic; Crosslinking.
*
Corresponding author. Tel.: C33 1 51 12 54 29; fax: C33 2 51 12 54 02;
e-mail: fabrice.odobel@chimie.univ-nantes.fr
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.07.094

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C. Monnereau et al. / Tetrahedron 61 (2005) 10113–10121
silyl: TMS and trisisopropylsilyl: TIPS). The selective
cleavage of the ethynyl protective groups allows for
successive Sonogashira cross-coupling reactions of the
porphyrin with the electron donor moiety and then with
the electron acceptor unit (Scheme 1). The preparation of
the starting porphyrin 6 is depicted in Scheme 2.
The bisbrominated porphyrin 2 is readily synthesized in
gram-scale following literature methodology. The con-
ditions used here were mostly inspired by those reported by
Plater,24 with a slight modification on the bis bromination
step. This reaction offers a higher yield when the
N-bromosuccinimide (NBS) was added dropwise and at
low temperature (90% yield) instead of in one fraction at
room temperature (70% yield).
Figure 1. Structures of the electro-optic materials described in this study.
acid group on the porphyrins makes it possible to
copolymerize them with GMA and to produce a material
that could be subsequently thermally crosslinked after
poling (Fig. 1).
We tested two different routes to prepare porphyrin 6
(Scheme 2). A straightforward approach consists in a
statistical Sonogashira cross-coupling reaction of porphyrin
2 with a mixture of trisisopropylsilyl acetylene and
trimethylsilyl acetylene, followed by a selective deprotec-
tion of the trimethylsilyl group under basic conditions, as
described by Therien.25 The second route requires the
preparation of the symmetrical bis trimethylsylilacetylene
porphyrin 4, followed by the cleavage of both trimethylsilyl
groups by fluoride. Then, the deprotonation of one ethynyl
group of 5 with lithium bis(trimethylsilyl)amide (LiHMDS)
and the quenching of the resulting anion with trisisopro-
pylsilyl chloride also afforded porphyrin 624 as analogous to
2. Results and discussion
The synthesis of the donor–acceptor porphyrins was
performed using a new converging approach, which differs
from the procedures originally described by Therien7 and
later used by Plater24 for the preparation of other arylethynyl
porphyrins.
The synthetic approach relies on a key synthon: the
bisethynyl porphyrin 3 in which the ethynyl groups are
protected with silyl groups of different labilities (trimethyl
Scheme 1. Retrosynthetic scheme for the synthesis of the push–pull porphyrin.
Scheme 2. Synthesis of the porphyrin 6. Reagents and conditions: (i) NBS (2 equiv), CH2Cl2, 0 8C, 90%; (ii) trisisopropylsilyl acetylene (6 equiv)/
trimethylsilyl acetylene (2 equiv), Pd(PPh3)2Cl2, CuI, Et3N, THF, 20 h, 40 8C, 40%; (iii) NaOH (1 M aq), THF/MeOH, rt, 88%; (iv) trimethylsilylacetylene
(5 equiv), Pd(PPh)3Cl2, THF, Et3N, 20H, 45 8C, 95%; (v) BuN4F, THF, rt, 92%; (vi) LiHMDS (1.4 equiv), THF, 10 min, then isoPr3SiCl (1.4 equiv), 38%.

C. Monnereau et al. / Tetrahedron 61 (2005) 10113–10121
10115
derivatives already exist in literature27,28, but few of them
operate in mild and neutral conditions compatible with the
free alcoholic group of 7. The iodination reaction used in the
synthesis of 8 was inspired by a method originally described
by Irie for the iodination of indole derivatives.29 It consists
in reacting an excess of iodine on the N-ethyl-N-
hydroxyethyl-aniline 7, in a mixture of pyridine–dioxane
(1/1). It appeared that these simple and mild conditions were
perfectly suitable for the selective iodination of compound 7
with an excellent 96% yield (Scheme 3). Compound 8 was
then reacted with methacryloyl chloride in the presence of
Et3N, affording 9 with a 70% yield. The Sonogashira cross-
coupling reaction of 9 with the porphyrin 6 was carried out
using Lindsey’s conditions30 because they gave higher yield
and higher reproducibility than those used by Plater.24 We
attribute this to the formation of two undesired by-products,
namely the compound 100 resulting from the Glaser’s
homocoupling and the compound 1000 in which the
acetylenic was transformed into vinyl alcohol group
following an anti-Markovnikov hydration type reaction31,32
(Scheme 4). Purification of the porphyrin 10 was not
possible by column chromatography on silica gel or alumina
due to the degradation of the zinc porphyrin. A size
exclusion chromatography on Sephadex LH20 stationary
phase was instead performed after a flash filtration on silica
gel initially neutralized by triethylamine. The trisisopropyl-
silyl group of 10 was finally cleaved by tetrabutylammo-
nium fluoride in a quantitative yield.
Scheme 3. Synthesis of the donor moiety 9 and its coupling with porphyrin
6. Reagents and conditions: (i) iodine (3 equiv), pyridine, dioxane, 1 h,
0 8C, 96%; (ii) methacryloyl chloride, CHCl3, Et3N, 0 8C, 70%;
(iii) Pd2(dba)3$CHCl3, AsPh3, THF/toluene/Et3N, 40 8C, 20 h, 85%;
(iv) Bu4NF, THF, rt, 99%.
Anderson’s similar species with trihexylsilylethynyl and
unsubsituted ethynyl groups.26 The two routes gave a
similar overall yield (38%), but the second route avoids the
utilization of the costly trisisopropylsylil acetylene reagent,
on the other hand the first route is one step shorter.
Various attempts to couple the easily available 4-bromo-N-
ethyl-N-hydroxyaniline with the porphyrin 6 failed. This
can be explained by the inefficient oxidative addition of
electron rich amino phenyl bromide on the Pd0 center of the
catalyst. This failure prompted us to replace the bromo
group by the more reactive iodo halogen. Numerous
approaches for the iodination in the para position of aniline
The iodinated acceptor moiety 13 was prepared from the
commercially available 2-amino-5-nitro-benzoic acid 12
according to a Sandmeyer reaction from the diazonium salt
of 12 and potassium iodide (Scheme 5). The Sonogashira
Scheme 4. Structure of the by-products 100 and 1000 formed during the reaction of 6 and 9 using the catalyst Pd(PPh3)4.
Scheme 5. Synthesis of the acceptor moieties 13 and 14 and coupling with porphyrin 11. Reagents and conditions: (i) NaOH (O, 5 N aq), 70 8C, then HCl
(12 N), then NaNO2, 0 8C; (ii) KI (satd aq), H2O, 0 8C, 65% for the two steps; (iii) tert-BuOH, DCC/DMAP, THF, 70 8C, 51%; (iv) Pd2(dba)3$CHCl3, AsPh3,
THF/toluene/Et3N, 40 8C, 20 h.

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C. Monnereau et al. / Tetrahedron 61 (2005) 10113–10121
Scheme 6. Polymerization reaction of the esterified push–pull porphyrin 17.
cross-coupling reaction of porphyrin 6 with 13 afforded the
expected product 15 with a 50% yield, but unfortunately the
lack of reproducibility of this reaction prevented us from
preparing the expected push–pull porphyrin 15 in large
quantity. This problem was not surprising, since
Mioskowsky and co-workers33 have shown that a carboxylic
acid in ortho position of an iodo group prevents Sonogashira
cross-coupling, most probably by the irreversible chelation
of the Pd catalyst by COOH after oxidative addition of aryl
iodide. We decided therefore, to protect the acid group by a
tert-butyl ester group. The esterification was carried out
by reacting 13 and tert-butanol in THF in the presence of
dicyclohexylcarbodiimide and a catalytic amount of
dimethylaminopyridine and afforded 14 in a quite satisfying
yield of 65%. Compound 14 was then successfully coupled
with porphyrin 11 in a Sonogashira cross-coupling reaction,
to give 16 in 85% yield (Scheme 5). Unfortunately, all our
attempts to deprotect selectively the tert-butyl group
without affecting the methacrylate function (including the
use of mild basic condition, trifluoroacetic acid, or cerium
chloride) failed. The best results were obtained using cerium
chloride chloroform but with only 15% yield.
standards) was performed on 17 and it showed a Mwof only
2400 D with a polydispersity index (PDI)Z1.2, indicating
an oligomeric structure rather than polymeric.
These unsatisfying results prompted us to direct our efforts
to a new porphyrin chromophore in which the position of the
respective nitro and carboxylic acid groups on the electron
acceptor moiety were inverted (compound 20). Previous
works on azo push–pull chromophores have indeed shown
that such a change did not affect significantly the value of
the electro-optic coefficient.34–36 In compound 19, the new
position of the carboxylic acid group with respect to the
iodo group should avoid the problem encountered in the
final Sonogashira cross-coupling step. In addition, the more
accessible carboxylic acid group, compared to that in the
original target 15, could facilitate the crosslinking reaction
with epoxy functions of the polymer.
The new acceptor moiety 19 was synthesized according to a
similar Sandmeyer reaction to that previously used for 13,
but using the commercially available 4-amino-3-nitro-
benzoic acid 18 as a starting material (Scheme 7). The
iodinated acceptor 19 was finally coupled with porphyrin 6
leading to 20 with an excellent 85% yield with high
reproducibility.
Still, we decided to copolymerize the protected esterified
porphyrin 16 with glycidyl methacrylate. The copolymeri-
zation was performed in THF with a molar ratio GMA/
chromophore of 95:5, using 10% mol AIBN as an initiator,
and leads to a total conversion of the monomer 16
(Scheme 6). A size exclusion chromatography (polystyrene
Copolymerization of 20 with GMA was performed in THF
with 10% mol. AIBN as an initiator and with an increased
amount of porphyrin 16 (15% mol) compared to that used in
Scheme 7. Synthesis of the acceptor moietie 19 and its coupling with porphyrin 11. Reagents and conditions: (i) NaOH (O, 5 N aq), 70 8C, then HCl (12 N),
then NaNO2, 0 8C; (ii) KI (satd aq), H2O, 0 8C, 65% for the two steps; (iii) Pd2(dba)3$CHCl, AsPh3, THF/toluene/Et3N, 40 8C, 20 h, 85%.

C. Monnereau et al. / Tetrahedron 61 (2005) 10113–10121
10117
Scheme 8. Polymerization reaction of the chromophore 20 with glycidyl methacrylate.
the case of 17. Precipitation of the crude reaction mixture
with methanol followed by a vacuum filtration afforded
polymer 21 with a 60% yield (Scheme 8). A size exclusion
chromatography was performed and indicated a satisfying
molecular weight MwZ8600 D with a polydispersity
indexZ1.6.
precoated with Merck 5735 Kieselgel 60F254. Column
chromatography was carried out either with 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. 5,15-Bis-(3,5-di-tert-butylphenyl)por-
phyrin was prepared according to literature method.37
ATG measurements performed on the push–pull chromo-
phore 20 and on the corresponding polymer 21 indicated no
degradation of both materials until 220 8C confirming the
high thermal stability of these substances.
UV–vis absorption spectra were recorded on a UV-2401PC
Shimadzu spectrophotometer. Fourier transform infrared
spectra were recorded in pressed KBr pellets on a Bruker
Vector 22 spectrometer.
Molecular masses and molecular mass distributions were
measured using size exclusion chromatography (SEC) on a
system equipped with a SpectraSYSTEM AS1000 auto-
sampler, with a guard column (Polymer Laboratories, PL
gel 5 m Guard, 50!7.5 mm) followed by two columns
(Polymer Laboratories, 2 PL gel 5 m MIXED-D columns,
2!300!7.5 mm), with a SpectraSYSTEM RI-150 detector
and a SpectraSYSTEM UV2000 detector. The eluent used
was THF at a flow rate of 1 mL minK1 at 35 8C. Polystyrene
standards [(580–483)!103 g molK1] were used to calibrate
the SEC. The purity of the compounds was better than 95%
3. Conclusion
This work is the first example of incorporation of a
porphyrin displaying NLO properties into a crosslinkable
polymeric matrix. Notably, the satisfying overall yield of
22% from the free base bis-aryl porphyrin 1 to the push–pull
chromophore 20, has been increased compared to that
reported in previous papers for simpler push–pull porphyrin
chromophores. The push–pull porphyrin 20 has been
successfully copolymerized with glycidyl methacrylate
leading to a soluble material. It is noteworthy that the
synthetic strategy described herein, allows for the prepa-
ration of significant quantity of both monomeric porphyrin
20 and polymer 17 permitting thus, a complete study of
the electro-optical properties of these new materials. The
investigation of the magnitude and the stability of the
electro-optical properties of these new materials is under
way and will be reported in due course.
1
as judged by H NMR spectroscopy.
4.1.1. [5,15-Dibromo-10,20-bis-(3,5-di-tert-butylphenyl)
porphyrinato] zinc (II): 2. Porphyrin 1 (1.21 g,
1.62 mmol) was dissolved in 60 mL of dichloromethane.
The mixture was cooled to 0 8C and NBS (560 mg,
3.16 mmol in 10 mL of dichloromethane) was added
dropwise with an addition funnel. The ice bath was removed
and methanol (200 mL) was added and the volume of
the resulting solution was reduced (roughly 20 mL). The
precipitate was filtered and intensively washed with
methanol to give a violet powder (1.31 g, 90%). The
analytical data of this compound agreed completely with
those reported by Plater.24
4. Experimental
4.1. General methods
1H NMR spectra were recorded on a ARX 400 MHz Bruker
spectrometer. Chemical shifts for 1H NMR spectra are
referenced relative to residual protium in the deuterated
solvent (CDCl3, dZ7.26 ppm; d-THF d1Z3.57 ppm–dZ
1.72 ppm). UV–vis absorption spectra were recorded on a
Cary 5G Varian spectrophotometer. Mass spectra were
recorded on a EI-MS HP 5989A spectrometer or on a JMS-
700 (JEOL LTD, Akishima, Tokyo, Japan) double focusing
mass spectrometer of reversed geometry equipped with
electrospray ionization (ESI) source. Thin-layer chroma-
tography (TLC) was performed on aluminum sheets
3
1H NMR (300 MHz, DMSO), d (ppm): 9.60 (d, 4H, JZ
4.2 Hz); 8.77 (d, 4H, 3JZ4.2 Hz); 7.97 (d, 4H, 4JZ1.5 Hz);
4
7.83 (t, 2H, JZ1.5 Hz); 1.57 (s, 36H).
4.1.2. [5,15-Bis-(3,5-di-tert-butylphenyl)-10-(trisisopro-
pylsilyl)ethynyl-20-(trimethylsilyl)ethynyl-porphyri-
nato] zinc (II): 3. Porphyrin 2 (300 mg, 0.33 mmol),
Pd(PPh3)2Cl2 (24 mg), CuI (7 mg), trimethylsilylacetylene
(100 mL, 0.7 mmol), trisisopropylsilyl acetylene (0.4 mL,

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C. Monnereau et al. / Tetrahedron 61 (2005) 10113–10121
3
1.78 mmol) were loaded in a sealed tube. THF (10 mL) and
Et3N (3 mL) were added and the mixture was stirred for
20 h at 40 8C. After evaporation of the solvents, the residue
was purified by flash column chromatography on silica gel
eluted with a gradient of petroleum ether/dichloromethane:
from 90:10 to 70:30. The middle green fraction was isolated
giving, after evaporation, the pure asymmetric disilylated
porphyrin 3 (135 mg, 40%).
1H NMR (300 MHz, CDCl3), d (ppm): 9.78 (d, 2H, JZ
4.8 Hz); 9.69 (d, 2H, 3JZ4.8 Hz); 8.99 (d, 2H, 3JZ4.8 Hz);
8.98 (d, 2H, 3JZ4.8 Hz); 8.03 (d, 4H, 4JZ1.8 Hz); 7.81 (t,
2H, 4JZ1.8 Hz); 4.19 (s, 1H); 1.55 (s, 36H); 1.51–1.42 (m,
21H). UV–vis (CH2Cl2): lmax, nm (3, molK1 L cmK1): 435
(205,000); 576 (9000); 630 (15,000). HR-ESMS, m/z: calcd
for C61H72N4SiZn: 952.484 (MC%), found: 952.485 (MC%).
4.1.5. 1-Iodo-4-[N-ethyl,N-(2-hydroxyethyl)amino]ben-
zene: 8. To a solution of N-ethyl,N-hydroxyethylaniline
(4 g, 24.2 mmol) in dioxane (180 mL) and pyridine
(180 mL) cooled in an ice bath, iodine (9.22 g,
36.2 mmol) was added. After 1 h of stirring the mixture
was warmed to room temperature for one further hour. Then
iodine (3 g, 13 mmol) was added and the mixture was stirred
for one supplementary hour. The crude reaction mixture was
washed with 10% aq Na2S2O3 until the brown color
disappeared. After addition of water, the mixture was
extracted with dichloromethane. The solvent was rotary-
evaporated and the residue was purified by flash column
chromatography on silica gel eluted with dichloromethane.
White crystals were obtained (6.52 g, 96%).38
3
1H NMR (300 MHz, CDCl3), d (ppm): 9.74 (d, 2H, JZ
4.8 Hz); 9.69 (d, 2H, 3JZ4.8 Hz); 8.98 (d, 2H, 3JZ4.8 Hz);
8.95 (d, 2H, 3JZ4.8 Hz); 8.03 (d, 4H, 4JZ1.8 Hz); 7.81 (t,
2H, 4JZ1.8 Hz); 1.54 (s, 36H); 1.51–1.42 (m, 21H); 0.59 (s,
9H). UV–vis (CH2Cl2): lmax, nm (3, molK1 L cmK1) 434
(210,000); 576 (9500); 629 (17,000). FT-IR (cmK1): 2960
(s, tert-Bu); 2141 (m, C^C); 1592 (m, Ar); 1213 (m); 852
(s). HR-ESMS, m/z: calcd for C64H80N4Si2Zn: 1024.521
(MC%), found: 1024.520 (MC%).
4.1.3. [5,15-Bis-(3,5-di-tert-butylphenyl)-10,20-bis-ethy-
nyl-porphyrinato] zinc (II): 5. Porphyrin 2 (1.01 g,
1.11 mmol), trimethylsilylacetylene (560 mL, 4.44 mmol),
CuI (21 mg), Pd(PPh3)2Cl2 (84 mg) were dissolved in THF
(40 mL) and Et3N (10 mL) in a Schlenk tube set under argon
atmosphere. The mixture was heated at 45 8C for 20 h. The
solvents were evaporated and the residue was filtered
through silica gel, eluted with dichloromethane/petroleum
ether: 50:50. The green solid was dissolved in THF
(100 mL) and Bu4NF 1 M in THF (2.5 mL, 2.5 mmol)
was added. The solvents were evaporated to 1/4 of the initial
volume and MeOH was added to precipitate the porphyrin.
After filtration and washing with methanol, porphyrin 5 was
obtained as a green-blue powder (790 mg, 90%).
1H NMR (300 MHz, CDCl3), d (ppm): 7.44 (d, 2H, JZ
3
8.7 Hz); 6.52 (d, 2H, 3JZ8.7 Hz); 3.77 (t, 2H, 3JZ5.7 Hz);
3
3.37–3.45 (m, 4H); 1.7 (s(broad), 1H); 1.14 (t, 3H, JZ
6.9 Hz). 13C NMR (300 MHz, CDCl3), d (ppm): 147.72;
137.81; 123.94; 114.92; 59.97; 52.44; 45.58; 11.72. EI-MS:
MC% (%): 293 (100); 263 (22); 247 (18); 136 (28); 92 (37).
MpZ33 8C.
4.1.6. 2-[Ethyl(4-iodophenyl)amino]ethyl methacrylate:
9. A two necked flask equipped with a reflux condenser and
an argon outlet was charged with 8 (5 g, 17.2 mmol) and
THF (75 mL). Et3N (3.62 mL) was added and the mixture
was cooled at 0 8C. Methacryloyl chloride (1.95 mL,
17.2 mmol) was added dropwise with a syringe over a
period of 1 h and the solution was then heated for 20 h at
40 8C. The solution was filtered, evaporated and the residue
was chromatographed on silica gel eluted with the mixture
dichloromethane/petroleum ether: 50:50. The pure desired
product was isolated as a colorless oil (4.25 g, 75%).
1H NMR (300 MHz, DMSO-d6), d (ppm): 9.68 (d, 4H, 3JZ
4.8 Hz); 8.90 (d, 4H, 3JZ4.8 Hz); 8.10 (d, 4H, 4JZ1.5 Hz);
7.92 (t, 2H, 4JZ1.5 Hz); 4.63 (s, 2H); 1.59 (s, 36H).
HR-ESMS, m/z: calcd for C52H52N4Zn: 796.351 (MC%),
found: 796.353 (MC%).
4.1.4. [5,15-Bis-(3,5-di-tert-butylphenyl)-10-ethynyl-20-
(trisisopropylsilyl)ethynyl-porphyrinato] zinc (II): 6.
Route 1. Porphyrin 3 was dissolved in a mixture of THF/
MeOH (15 mL/15 mL). 1 M aq NaOH (2 mL) was added
and the mixture was stirred at room temperature for 15 min.
Dichloromethane and water were then added and the
organic layer was extracted, dried and rotary-evaporated.
The residue was dissolved in a minimum amount of
dichloromethane, precipitated with methanol and filtered.
Porphyrin 6 was obtained as a green solid (110 mg, 88%).
3
1H NMR (300 MHz, CDCl3), d (ppm): 7.47 (d, 2H, JZ
9.0 Hz); 6.54 (d, 2H, 3JZ9.0 Hz); 6.08 (s, 1H); 5.58 (s, 1H);
3
3
4.28 (t, 2H, JZ6.3 Hz); 3.58 (t, 2H, JZ6.3 Hz); 3.45 (q,
2H, 3JZ7.2 Hz); 1.91 (s, 3H); 1.14 (t, 3H, 3JZ7.2 Hz). 13
C
NMR (300 MHz, CDCl3), d (ppm): 166.25; 146.13; 136.76;
134.96; 127.99; 124.92; 113.25; 60.78; 47.46; 44.11; 17.30;
11.01. FT-IR (cmK1): 2895–2970 (w, alk); 1717 (s, C]O);
1637 (w, CH2]C); 1587 (m, Ar); 1163 (s). EI-MS: MC%
(%): 359 (24); 260 (100).
Route 2. Porphyrin 5 (500 mg, 0.63 mmol) was dissolved in
distilled THF (60 mL). Bistrimethylsilyl-lithium bis(tri-
methylsilyl)amide (LiHMDS) 1 M in THF (0.9 mL,
0.9 mmol) was rapidly added (in one portion) to the stirred
mixture. After 10 min at room temperature, trisisopropylsi-
lyl chloride (0.25 mL) was added and the mixture was
further stirred for 10 min. 30 mL of 1 M aq KOH were
added and the mixture was extracted with dichloromethane.
After removal of the solvent, the residue was purified by
flash chromatography on silica gel eluted with the mixture
petroleum ether/dichloromethane: 80:20 leading to the
awaited porphyrin 6 (230 mg, 38%).
4.1.7. {5,15-Bis-(3,5-di-tert-butylphenyl)-10-[ethyl-
(methacryloyloxyethyl)aminophenylethynyl]-20-(trisiso-
propylsilyl)ethynyl-porphyrinato} zinc (II): 10. Por-
phyrin 6 (300 mg, 0.315 mol) and compound 9 (224 mg,
0.630 mol) were placed in a schlenk tube and toluene
(30 mL), THF (10 mL) and Et3N (10 mL) were added. The
solution was deaerated by three freeze–pump–thaw cycles
and Pd2(dba)3$CHCl3 (30 mg) and triphenylarsine (30 mg)
were added. The solution was stirred 30 min at room
temperature. After solvents removal, the residue was

C. Monnereau et al. / Tetrahedron 61 (2005) 10113–10121
10119
dissolved in THF and chromatographied on LH 20
4.2. General procedure for iodination of amino nitro-
benzoic acid (compound 13 or 19)
Sephadex stationary phase and the major green band was
collected. Finally, the green powder was dissolved in a
minimum volume of dichloromethane and precipitated with
methanol. After filtration, a green powder was obtained
(320 mg, 85%).
A solution of the amino nitrobenzoic acid 12 or 18 (4.5 g,
24.7 mmol) in 45 mL of 0.5 M aq NaOH was heated at
70 8C until complete dissolution. Then, 10 mL of 12 N HCl
were added dropwise, giving rise to a fine precipitate. The
mixture was then cooled at 0 8C with an ice bath and NaNO2
(1.7 g, 21.7 mmol) in 5 mL of water was added. The
precipitate partly dissolved and the mixture was stirred for
1 h at 0 8C. The mixture was filtered while the filtrate was
carefully kept at 0 8C. Then, a saturated solution of KI
(8.4 g, 50 mmol) was added dropwise on the precipitate
causing a strong release of N2. The mixture turned to red and
a precipitate appeared. The ice bath was removed and the
mixture was stirred for two additional hours. After filtration
and washing with water, the iodo nitrobenzoic acid was
obtained as an orange solid (4.7 g, 65%).
3
1H NMR (300 MHz, CDCl3), d (ppm): 9.77 (d, 2H, JZ
4.8 Hz); 9.72 (d, 2H, 3JZ4.5 Hz); 8.94 (m, 4H); 8.05 (d, 4H,
3
4
4JZ1.8 Hz); 7.87 (d, 2H, JZ9.0 Hz); 7.81 (t, 2H, JZ
1.8 Hz); 6.88 (d, 2H, 3JZ9.0 Hz); 6.14 (s, 1H); 5.62 (s, 1H);
3
3
4.38 (t, 2H, JZ6.3 Hz); 3.72 (t, 2H, JZ6.3 Hz); 3.55 (q,
2H, 3JZ7.2 Hz); 1.97 (s, 3H); 1.4–1.6 (m, 57H); 1.25 (t, 3H,
3JZ7.2 Hz). FT-IR (cmK1): 2960 (s, t-Bu); 2930 (s, i-Pr);
2863 (m, –CH2–); 2183 (m, C^C); 2136 (m, C^C);
1718 (m, C]O); 1212 (s). HR-ESMS, m/z: calcd for
C75H89N5O2SiZn: 1183.608 (MC%), found: 1183.609
(MC%).
4.2.1. 2-Iodo-5-nitrobenzoic acid 13.39,40 1H NMR 13
(300 MHz, CDCl3), d (ppm): 8.83 (d, 1H, 4JZ2.7 Hz); 8.30
(d, 1H, 3JZ8.7 Hz); 8.02 (dd, 1H, 3JZ8.7 Hz, 4JZ2.7 Hz);
6.3 (s broad, 1H). FT-IR (cmK1): 1710 (s, C]O); 1526 (s,
nasym NO2); 1347 (s, nsym NO2). EI-MS: MC% (%): 293
(100); 263 (36); 92 (35). MpZ197 8C.
When Plater’s conditions were used (mixture of tetrahydro-
furane (6 mL) and pyrrolidine (20mL) as solvents) and the
above catalyst (Pd2(dba)3$CHCl3 and triphenylarsine) was
replaced by Pd(PPh3)4 (6 mg) and CuI (3 mg)) the two
major products were formed. These two products were the
porphyrins 100 and 1000 that were isolated in variable yields
from one run to the other 100 (70–50%) and 1000 (10–30%).
4.2.2. 4-Iodo-3-nitrobenzoic acid 19.41,42 1H NMR 18
(300 MHz, CDCl3), d (ppm): 8.52 (d, 1H, 4JZ1.5 Hz); 8.21
(d, 1H, 3JZ6.0 Hz); 7.94 (dd, 1H, 3JZ6.0 Hz, 4JZ1.5 Hz);
4.8 (s broad, 1H). FT-IR (cmK1): 1700 (s, C]O); 1535
(s, nasym NO2); 1351 (s, nsym NO2). EI-MS: MC% (%): 293
(100); 263 (25); 136 (32); 92 (40). MpZ201 8C.
Porphyrin dimer 100. 1H NMR (300 MHz, CDCl3), d (ppm):
4
9.73 (m, 8H); 8.91 (m, 8H); 8.02 (d, 8H, JZ1.8 Hz); 7.80
4
(t, 4H, JZ1.8 Hz); 1.4–1.6 (m, 114H).
Porphyrin 1000. 1H NMR (300 MHz, CDCl3), d (ppm): 10.44
3
3
(s, 1H, CHO); 9.78 (d, 2H, JZ4.5 Hz); 9.42 (d, 2H, JZ
4.5 Hz); 9.05 (d, 2H, 3JZ4.5 Hz); 9.01 (d, 2H, 3JZ4.5 Hz);
4.2.3. tert-Butyl 2-iodo-5-nitrobenzoate: 14. Compound
13 (1.75 g, 6 mmol) was dissolved in THF (36 mL).
Dicyclohexylcarbodiimide (DCC, 1.85 g, 6.9 mmol) and
tert-BuOH (2.83 mL, 30 mmol) were added. DMAP
(20 mg) were added and the mixture was heated for 20 h
at 70 8C. The solvents were removed and the residue was
purified by a column chromatography on silica gel eluted
with the mixture dichloromethane/petroleum ether: 30:70.
The pure product 14 was isolated as white crystals (1.35 g,
65%).
8.04 (d, 4H, JZ1.8 Hz); 7.80 (t, 2H, 4JZ1.8 Hz); 5.98 (s,
4
2H); 1.4–1.6 (m, 57H). FT-IR (cmK1): 2956–2900 (vs, t-Bu,
i-Pr); 2864 (m, –CH2–); 2810 and 2710 (w, CO–H); 2138
(m, C^C); 1724 (m, C]O). MS(MALDI-TOF), m/z: calcd
for C61H72N4OSiZn: 970.492 (MC%), found: 970 (77%),
971 (48%), 972 (100%), 973 (72%), 974 (74%), 975 (35%).
4.1.8. {5,15-Bis-(3,5-di-tert-butylphenyl)-10-ethynyl-20-
[ethyl(methacryloyloxyethyl) aminophenylethynyl]-por-
phyrinato} zinc (II): 11. One hundred and fifty microlitres
of 1 M Bu4NF in THF (0.15 mmol) was added to a solution
of porphyrin 10 (150 mg, 0.126 mmol in 150 mL of THF).
The mixture was stirred for 30 min at room temperature.
The solvent was partly removed, water was added and the
mixture was extracted with dichloromethane. After evapo-
ration of the solvents, the residue was redissolved in a
minimum amount of dichloromethane, petroleum ether was
added to precipitate the porphyrin (130 mg, 100%).
4
1H NMR (300 MHz, CDCl3), d (ppm): 8.47 (d, 1H, JZ
3.1 Hz); 8.16 (d, 1H, 3JZ8.7 Hz); 7.93 (dd, 1H, 3JZ8.7 Hz,
4JZ3.1 Hz); 1.65 (s, 9H). 13C NMR (300 MHz, CDCl3), d
(ppm): 164.22; 147.69; 142.30; 138.71; 125.69; 124.89;
101.83; 84.20; 28.07. FT-IR (cmK1): 2980 (m, tert-Bu);
1713 (s, C]O); 1526 (s, nasym NO2); 1341 (s, nsym NO2).
EI-MS: MC% (%): 349 (16); 293 (97); 276 (38); 75 (36); 57
(89); 56 (100). MpZ107 8C.
3
1H NMR (300 MHz, CDCl3), d (ppm): 9.74 (d, 2H, JZ
4.2.4. {5,15-Bis-(3,5-di-tert-butylphenyl)-10-(4-nitro-2-
carboxyphenyl)ethynyl-20-[ethyl (methacryloyloxy-
ethyl)aminophenylethynyl]-porphyrinato} zinc (II): 15.
Porphyrin 11 (75 mg, 0.073 mmol) and compound 13
(25 mg, 0.085 mmol) were dissolved in THF (2 mL),
Et3N (2 mL) and toluene (6 mL). The mixture was
intensively degassed with three freeze–pump–thaw cycles.
Pd2(dba)3$CHCl3 (7 mg) and AsPh3 (7 mg) were added and
the mixture was heated for 2 h at 50 8C. The crude reaction
mixture was filtered through a short plug of celite and the
4.8 Hz); 9.64 (d, 2H, 3JZ4.5 Hz); 8.96 (m, 4H); 8.06 (d, 4H,
3
4
4JZ1.8 Hz); 7.82 (d, 2H, JZ9.0 Hz); 7.80 (t, 2H, JZ
1.8 Hz); 6.85 (d, 2H, 3JZ9.0 Hz); 6.13 (s, 1H); 5.61 (s, 1H);
3
3
4.38 (t, 2H, JZ6.3 Hz); 4.06 (s, 1H); 3.71 (t, 2H, JZ
6.3 Hz); 3.54 (q, 2H, 3JZ7.2 Hz); 1.97 (s, 3H); 1.4–1.6 (m,
57H); 1.28 (t, 3H, 3JZ7.2 Hz). FT-IR (cmK1): 2960 (s, tert-
Bu); 2863 (m, –CH2–); 2138 (m, C^C); 1718 (m, C]O);
1212 (s). UV–vis (CH2Cl2): lmax, nm (3, molK1 L cmK1):
432 (205,000); 568 (11,000); 616 (10,000).

10120
C. Monnereau et al. / Tetrahedron 61 (2005) 10113–10121
solvents were removed. The crude porphyrin was dissolved
in a minimum amount of dichloromethane and was
precipitated with petroleum ether. Porphyrin 15 was
obtained as a green-brown powder upon vacuum filtration.
(43 mg, 51%).
(d, 2H, 3JZ9 Hz); 6.97 (d, 2H, 3JZ9 Hz); 6.11 (s, 1H); 5.60
(s, 1H); 4.40 (t, 2H, 3JZ6 Hz); 3.78 (t, 2H, 3JZ6 Hz); 3.58
3
(q, 2H, JZ5 Hz); 1.95 (s, 3H); 1.58 (s, 36H); 1.28 (t, 3H,
3JZ5 Hz). UV–vis (CH2Cl2): lmax, nm (3, molK1 L cmK1):
463 (125,000); 691 (52,000). FT-IR (cmK1): 2961 (s, t-Bu);
2867 (m, –CH2–); 2168 (m, C^C); 1742 (s, C]O acid);
1718 (m, C]O); 1518 (s, nasym NO2); 1342 (s, nsym NO2);
1212 (s, ns, C–O). HR-ESMS, m/z: calcd for
C73H72N6O6Zn: 1193.488 ([MCH]C%), found: 1193.487
([MCH]C%)
3
1H NMR (300 MHz, THF), d (ppm): 10.03 (d, 2H, JZ
4.2 Hz); 9.68 (d, 2H, 3JZ4.2 Hz); 8.98 (d, 1H, 3JZ1.8 Hz);
8.85 (d, 2H, 3JZ4.2 Hz); 8.82 (d, 2H, 3JZ4.2 Hz); 8.48 (dd,
1H, 3JZ4.8 Hz, 4JZ1.8 Hz); 8.45 (d, 1H, 3JZ4.8 Hz); 8.08
4
3
(d, 4H, JZ1.2 Hz); 7.85–7.92 (m, 4H); 6.98 (d, 2H, JZ
8.7 Hz); 6.08 (s, 1H); 5.61 (s, 1H); 4.42 (t, 2H, 3JZ5.2 Hz);
3.75 (t, 2H, 3JZ5.2 Hz); 3.57 (m, 2H); 1.94 (s, 3H); 1.58 (s,
36H); 1.35 (t, 3H, 3JZ5.7 Hz). UV–vis (CH2Cl2): lmax, nm
(3, molK1 L cmK1) 458 (123,000); 686 (48,000). FT-IR
(cmK1): 2961 (s, tert-Bu); 2867 (m, –CH2–); 2181 (s,
C^C); 1750 (s, C]O acid); 1718 (m, C]O ester) ; 1525
(s, nasym NO2); 1348 (s, nsym NO2); 1191 (s, ns, C–O). HR-
ESMS, m/z: calcd for C73H72N6O6Zn: 1193.488 ([MC
H]C%), found: 1193.486 ([MCH]C%).
4.3. General procedure for porphyrin polymerization
with glycidyl methacrylate (polymers 17 and 21)
A mixture of porphyrin (16 or 20) and glycidyl methacrylate
(with a molar ratio porphyrin/GMA of 1:19 and 1:6, for
respectively 17 and 21) was dissolved in THF (25 mL/
1 mmol porphyrin) in a sealed tube. AIBN was added (10%
weight of the monomers) and the mixture was degassed
by three freeze–pump–thaw cycles. The mixture was heated
at 70 8C for 20 h. The mixture was added dropwise in 10
volumes of methanol to precipitate the polymer. The
precipitate was filtered and intensively washed with
methanol affording the polymer as a green powder.
4.2.5. {5,15-Bis-(3,5-di-tert-butylphenyl)-10-(4-nitro-2-
tert-butylcarboxyphenyl)ethynyl-20-[ethyl (methacryl-
oyloxyethyl)aminophenylethynyl]-porphyrinato} zinc
(II): 16. Porphyrin 11 (225 mg, 0.22 mmol) and 14
(114 mg, 0.33 mmol) were dissolved in THF (6 mL),
Et3N (6 mL) and toluene (20 mL). The mixture was
intensively degassed with three freeze–pump–thaw cycles.
Pd2(dba)3$CHCl3 (20 mg) and AsPh3 (20 mg) were added
and the mixture was heated for 12 h at 50 8C. The crude
reaction mixture was evaporated and the residue was
purified by flash chromatography on silica gel using the
mixture petroleum ether/dichloromethane: 30:70. The
porphyrin was dissolved in a minimum amount of
dichloromethane and was precipitated with methanol
affording a green-brown powder (235 mg, 85%).
4.3.1. Polymer 17. Yield: 80%, 280 mg. 1H NMR
(300 MHz, CDCl3), d (ppm): 9.7–9.9 (m, 4H); 8.7–8.9 (m,
4H); 7.95–8.05 (m, 4H); 7.7–7.8 (m, 4H); 6.8–6.9 (m, 2H);
4.4–4.2 (m, 19H); 3.8–3.6 (m, 21H); 3.05–3.2 (m, 19H);
2.7–2.9 (m, 19H); 2.5–2.6 (m, 19H); 1.8–2.0 (m, 20H); 0.8–
1.6 (m, 140H). FT-IR (cmK1): 2961 (m); 2181 (w, C^C);
1731 (s); 1148 (s); 907 (m, nas, epoxy). GPC averages:
(Mn)Z1900; (Mw)Z2400; PDIZ1.2.
4.3.2. Polymer 21. Yield: 58%, 250 mg. 1H NMR
(300 MHz, CDCl3), d (ppm): 9.7–9.9 (m, 4H); 8.8–9.0 (m,
4H); 7.6–8.2 (m, 8H); 6.8–7.0 (m, 2H); 4.4–4.2 (m, 11H);
3.8–3.6 (m, 13H); 3.05–3.2 (m, 11H); 2.5–2.9 (m, 22H);
0.8–2 (m, 80H). FT-IR (cmK1): 2956 (m); 2178 (w, C^C);
1730 (s); 1150 (s); 908 (m, nas, epoxy). GPC averages:
(Mn)Z5100; (Mw)Z8618; PDIZ1.6.
1H NMR (300 MHz, THF), d (ppm): 9.94 (d, 2H, 3JZ
4.5 Hz); 9.66 (d, 2H, 3JZ4.5 Hz); 8.85 (m, 3H); 8.77 (d, 2H,
3JZ4.5 Hz); 8.50 (dd, 1H, JZ4.8 Hz, JZ1.8 Hz); 8.40
(d, 1H, 3JZ4.8 Hz); 8.05 (d, 2H, 4JZ1.2 Hz); 7.8 (m, 4H);
6.92 (d, 2H, 3JZ8.7 Hz); 6.04 (s, 1H); 5.54 (s, 1H);
3
4
3
3
4.32 (t, 2H, JZ5.2 Hz); 3.72 (t, 2H, JZ5.2 Hz); 3.57 (q,
3
2H, JZ5.2 Hz); 1.88 (s, 3H); 1.75 (s, 9H); 1.52 (s, 36H);
Acknowledgements
3
1.22 (t, 3H, JZ5.2 Hz). UV–vis (CH2Cl2): lmax, nm (3,
molK1 L cmK1) 465 (110,000); 689 (56,000). FT-IR (cmK1):
2960 (vs, t-Bu); 2867 (m, –CH2–); 2183 (s, C^C); 1724 (s,
COOtBu); 1718 (m, C]O); 1524 (s, nasym NO2); 1348 (s,
nsym NO2); 1200 (s, ns, C–O). HR-ESMS, m/z: calcd for
C77H81N6O6Zn: 1249.551 ([MCH]C%), found: 1249.552
([MCH]C%).
The authors thank the Region des Pays de la Loire (CPER
18007) for the financial support of this program (fellowship
for C. M.).
References and notes
4.2.6. {5,15-Bis-(3,5-di-tert-butylphenyl)-10-(2-nitro-4-
carboxyphenyl)ethynyl-20-[ethyl (methacryloyloxy-
ethyl)aminophenylethynyl]-porphyrinato} zinc (II): 20.
The same protocol as used for 15 was applied, with 200 mg
of porphyrin 11, 65 mg of 19, 20 mL of toluene, 6 mL of
Et3N and 6 mL of THF. Porphyrin 20 was obtained as a
brown solid (208 mg, 87%).
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