Synthesis of bis(phenylethynyl)arylene-linked diporphyrins designed for studies of intramolecular energy transfer

Article abstract of DOI:10.1055/s-1999-3525

A series of donor-bridge-acceptor systems has been designed to give information on how the medium between the donor and the acceptor influences the excitation energy transfer process. The donor and the acceptor are zinc and free base porphyrins, respectiv

Full text of DOI:10.1055/s-1999-3525

PAPER
1155
Synthesis of Bis(phenylethynyl)arylene-Linked Diporphyrins Designed for
Studies of Intramolecular Energy Transfer
Johan Kajanus,a Sofia B van Berlekom,a Bo Albinsson,b Jerker Mårtensson*a
a Department of Organic Chemistry, Chalmers University of Technology, SE-412 96 Göteborg, Sweden
b Department of Physical Chemistry, Chalmers University of Technology, SE-41296 Göteborg, Sweden
Fax +46(31)7723657; E-mail: jerker@oc.chalmers.se
Received 22 December 1998; revised 3 March 1999
the coupling depends on the energies of the lowest excited
states of such a bridge in comparison with corresponding
energies of the donor and acceptor. Diporphyrin donor-ac-
ceptor systems with large p-conjugated bridges have been
Abstract: A series of donor-bridge-acceptor systems has been de-
signed to give information on how the medium between the donor
and the acceptor influences the excitation energy transfer process.
The donor and the acceptor are zinc and free base porphyrins, re-
spectively. The systems were obtained by a synthetic strategy that prepared and studied with respect to the geometry and dis-
guarantees a precise state of metalation, i.e. by a building block ap-
tance dependence of the excitation energy or electron
transfer.5
proach in which a third chromophore is formed as the two porphy-
rins are covalently linked together in a geometrically well defined
In this paper, we report the synthesis of a series of dipor-
phyrin donor-bridge-acceptor (D-B-A) systems designed
to give information on how the energetics of the bridge,
i.e. the medium between the donor and acceptor, influenc-
es excitation energy transfer. In addition to this primary
purpose our design of the D-B-A systems was based on
two general considerations: ease of preparation and ease
of interpretation of photophysical data6 obtained from the
systems. The D-B-A systems were thus given the follow-
ing features (Figure): The medium between donor (zinc
porphyrin) and acceptor (free base porphyrin) was varied
by covalently linking the porphyrins together with differ-
ent bridge chromophores. The tert-butyl groups (I) pro-
vide the facial encumbrance necessary for good solubility.
The methyl groups in the b position (II) force the planes
of the porphyrin and the phenyl ring to be nearly perpen-
dicular and interchromophore conjugation is thereby min-
imized to preserve the identity of the three chromophores.
Triple bonds (III) give geometrically well defined sys-
tems, which simplifies the interpretation of photophysical
data, and provide established coupling methods by which
the D-B-A systems were assembled. Finally the donor-ac-
ceptor distance was kept the same throughout the series in
order to facilitate immediate comparisons.
structure. The porphyrins are linked by one of the three different
bridge chromophores; 9,10-bis(phenylethynyl)anthracene, or 1,4-
bis(phenylethynyl)-substituted benzene or naphthalene. The differ-
ent units were assembled using copper-free, palladium-catalyzed
cross-coupling of aryl iodides with terminal alkynes. Reference
compounds that correspond to different parts of the systems have
also been prepared.
Key words: porphyrin; molecular design; palladium; cross-cou-
pling; donor-bridge-acceptor systems
The preparation of porphyrin arrays is an important area
of research, not only for mimicry of different biological
processes and elucidation of their mechanisms, but also
for the development of molecular electronic devices. In
recent years, one of the major tasks has been to prepare ar-
rays of chromophores to probe the electronic communica-
tion, i.e. electronic coupling, between the chromophores.
Electronic coupling between chromophores is the basis of
electron and excitation energy transfer from a donor to an
acceptor,1 two important transfer reactions crucial to nat-
ural photosynthesis2 and molecular devices.3 The elec-
tronic coupling between a donor and an acceptor has been
shown to be enhanced by p-conjugated bridges linking
donor and acceptor together.4 However, a systematic
study has not yet been reported on how the magnitude of
III
I
II
N
HN
N
N
N
N
N
Zn
Ar
NH
Bridge Chromophore
Figure Structure of the synthesized D-B-A systems consisting of a donor (zinc porphyrin), a bridged chromophore, and an acceptor (free
base porphyrin). ZnP-BB-H2P (Ar = 1,4-phenylene), ZnP-NB-H2P (Ar = 1,4-naphthylene), ZnP-AB-H2P (Ar = 9,10-anthrylene)
Synthesis 1999, No. 7, 1155–1162 ISSN 0039-7881 © Thieme Stuttgart · New York

1156
J. Kajanus et al.
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The phenylene system, ZnP-BB-H2P, was prepared in a
straightforward synthesis from the mono-protected p-
di(ethynyl)benzene 9, zinc iodoporphyrin 3 and free base
iodoporphyrin 4 (see Scheme 2). Unfortunately, the other
two systems could not be prepared using the same syn-
thetic protocol. Attempts were made to prepare trimethyl-
silyl-protected naphthalene and anthracene analogs of 9,
but this failed due to polymerization. It is known that 1,4-
diethynylnaphthalene readily polymerizes in the presence
of light,7 even in the solid state, and also the mono-silylat-
ed form appears to be highly light and heat sensitive.
Thus, the ethynyl group had to be on the porphyrin in the
preparation of the naphthylene and anthrylene systems,
ZnP-NB-H2P and ZnP-AB-H2P. These systems were
prepared from zinc ethynylporphyrin 7 and 1,4-di-
iodonaphthalene, and 9,10-diiodoanthracene, respectively
(see Scheme 3).
N
N
N
N
M
X
X =
X =
Si
5 M = 2 H
6 M = Zn
1 M = 2 H
2 M = Zn
Bu4NF, THF, r.t., 1h
86 %
X =
X =
I
A similar approach has been used by Kawabata et al. to
prepare a derivative of the phenylene linked diporphyrin
ZnP-BB-H2P from an ethynylporphyrin and 1,4-diiodo-
benzene.5a A disadvantage of this protocol is that when
ethynylporphyrins participate in palladium-catalyzed
cross-coupling reactions they can form butadiyne-linked
dimers via homocoupling. The butadiyne-linked dimers
can be troublesome byproducts as they may be difficult to
remove from the desired products. However, this side re-
action is suppressed by using proper reaction conditions in
the assembling of the D-B-A systems.8 In the course of
this work we have observed that the palladium-catalyzed
cross-coupling of zinc porphyrins work better compared
to when the same reaction is performed with the corre-
sponding free base porphyrin. For example, zinc porphy-
rin 12N could be prepared from zinc ethynylporphyrin 7
and 1,4-diiodonaphthalene in 27% yield. However, in an
attempt to prepare free base porphyrin 13N directly from
the free base ethynylporphyrin and 1,4-diiodonaphtha-
lene, using the same conditions as in the preparation of
12N, only ca 5% of 13N could be isolated. Zinc porphy-
rins seem to have a small co-catalytic effect that is observ-
able when the cross-coupling is performed under mild
conditions. Therefore, a zinc porphyrin was introduced in
the first step in the preparation of the D-B-A systems. In
this way a zinc porphyrin is present in both of the palladi-
um-catalyzed steps. A possible explanation to this obser-
vation is that Ph3P or Ph3As coordinates to the zinc
porphyrin which acts as a scavenger for free ligands. This
has been shown to be the co-catalytic effect of copper in
the Stille coupling.9
3 M = Zn
4 M = 2 H
7 M = Zn
Scheme 1
1-Ethynyl-4-[(triisopropylsilyl)ethynyl]benzene13 (9) was
prepared in two steps from 4-bromoacetophenone
(Scheme 2). In the first step, 4-bromoacetophenone was
converted to 4-[(triisopropylsilyl)ethynyl]acetophenone
(8) by cross-coupling with (triisopropylsilyl)acetylene
following a procedure similar to that used by Takahashi et
al. in the preparation of the trimethylsilyl-protected ana-
logue.14 Then, the methyl ketone was converted to a ter-
minal alkyne using the procedure of Negishi et al.15
affording 9. When trimethylsilyl was used as a protecting
group, the acetylide ion formed by treating the ketone
with lithium diisopropylamide and diethyl chlorophos-
phate attacked the trimethylsilyl group and a mixture of
non-, mono-, and disilylated dialkyne was obtained. 9,10-
Diiodoanthracene was prepared from 9,10-dibromoan-
thracene by lithiation followed by iodinolysis.16 1,4-Dii-
odonaphthalene
was
obtained
from
1,4-
dibromonaphthalene using the same procedure but in this
case, the use of more than 4 equivalents of tert-butyllithi-
um was necessary to drive the formation of the intermedi-
ate dilithio compound to completion.
The D-B-A systems were then assembled using the reac-
tion conditions developed by Wagner et al.,8 i.e. treatment
with Pd2(dba)3◊CHCl3/Ph3As (dba = dibenzylideneace-
tone) in a mixture of toluene and triethylamine at 40°C
(Schemes 2 and 3). The bridge building block 9 was react-
ed with zinc iodoporphyrin 3, the resulting porphyrin was
deprotected and zinc ethynylporphyrin 11 was coupled
with free base iodoporphyrin 4 affording ZnP-BB-H2P.
The synthesis of the different systems started with the
preparation of the appropriate building blocks. The por-
phyrins were prepared by acid-catalyzed condensation of
3,3’-diethyl-4,4’-dimethyl-2,2’-dipyrrylmethane10
and
functionalized benzaldehydes,11 followed by oxidation.12
The free base porphyrin 5 was converted to zinc porphyrin
6 and then deprotected with tetrabutylammonium fluoride
to zinc ethynylporphyrin 7 (Scheme 1).
The coupling products were obtained in decent yields (65
and 62%) using a reaction time of 4 hours. The coupling
reactions of the naphthyl and anthryl iodides were slower.
In the first step in the preparation of ZnP-NB-H2P and
ZnP-AB-H2P, zinc ethynylporphyrin 7 was treated with a
Synthesis 1999, No. 7, 1155–1162 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Bis(phenylethynyl)arylene-Linked Diporphyrins
1157
O
O
a
b
Br
TIPS
TIPS
98 %
69 %
c
8
9
d
65 %
N
N
N
Zn
TIPS
N
10
e
74 %
f
N
N
N
N
Zn
ZnP-BB-H2P
62 %
11
Scheme 2 Reagents and conditions: (a) (triisopropylsilyl)acetylene, (Ph3P)4Pd (5 mol%), CuI (10 mol%), Et3N, reflux, 2 h;14 (b) LDA, THF, –
78°C, 1 h; (EtO)2P(O)Cl, –78°C to r. t., 3 h; LDA, –78°C to r.t., 2.5 h;15 (c) Ref. 13; (d) 3, Pd2(dba)3◊CHCl3, Ph3As, toluene/Et3N (3:1), 40°C,
4 h; (e) Bu4NF, THF, r.t.; 1 h; (f) 4, Pd2(dba)3◊CHCl3, Ph3As, toluene/Et3N (3:1), 40°C, 4 h
five-fold excess of 1,4-diiodonaphthalene and 9,10-di- iodobenzene, 1,4-diiodonaphthalene, and 9,10-diiodoan-
iodoanthracene, respectively (Scheme 3). The building thracene, respectively. Following flash chromatography
blocks 12 were obtained in low but synthetically useful (silica gel, pentane/toluene 10:1) the bridge chro-
yields (27 and 48%) by heating the reaction mixture to mophores were isolated in 63–92% yield. The building
40°C for 4 days. Attempts were also made to prepare the blocks 15 were prepared by the same procedure using a
building blocks 12 at reflux temperature but this led to a three-fold excess of the diiodoaryls; 15 were then coupled
complex mixture of compounds both when Ph3P and with zinc ethynylporphyrin 7 affording reference porphy-
Ph3As were employed as a ligand. The zinc iodoporphy- rins 16. The zinc reference porphyrins were demetalated
rins 12 were demetalated to the corresponding free base to the corresponding free base porphyrins 17.
iodoporphyrins 13. These were then coupled with zinc
ethynylporphyrin 7 (Scheme 3). This route was chosen in
order to facilitate the purification of the final products,
ZnP-NB-H2P and ZnP-AB-H2P, because it was easy to
Et2O, toluene and THF were dried by distillation from sodium/ben-
zophenone under N2. CH2Cl2, Et3N and MeCN were dried by distil-
lation from CaH2 under N2. Dried solvents were used immediately
remove di(zinc porhyrin) dimers from the D-B-A systems
using CH2Cl2 on silica gel, whereas di(free base porphy-
rin) dimers had a chromatographic mobility comparable
to that of the D-B-A systems. This means, that any
butadiyne linked dimer formed as a byproduct in the
cross-coupling reaction of 13 and zinc ethynylporphyrin
7, was a di(zinc porphyrin) which was easy to separate
from the D-B-A systems ZnP-NB-H2P and ZnP-AB-
H2P.
after distillation. Commercially available reagents were used with-
out further purification. Column chromatography of zinc porphy-
rins and porphyrin dimers was performed using silica gel (Merck,
grade 60, 70–230 mesh). Flash chromatography was performed us-
ing silica gel (Matrex LC 60 Å / 35–70 micron). Size exclusion
chromatography (SEC) was performed using BioRad Bio-Beads S-
1
X3 in toluene. H (400 MHz) and 13C (100.6 MHz) NMR spectra
were recorded at r.t. with CDCl3 as solvent, using a Varian UNITY-
400 NMR spectrometer. Chemical shifts are reported relative to
TMS (dH 0) and CDCl3 (dC 77.0). Mass spectra were recorded using
a VG ZabSpec instrument. Porphyrin containing substances were
analyzed by positive FAB-MS (matrix 3-nitrobenzyl alcohol), other
substances were analyzed by EI-MS (70 eV). Deaeration of reaction
mixtures was performed by bubbling argon through the solution for
30 min. All palladium-catalyzed reactions were performed under ar-
gon atmosphere, palladium-catalyzed reactions involving porphy-
rins were performed in the dark. 3,3’-Diethyl-4,4’-dimethyl-2,2’-
dipyrrylmethane,10 3,5-di-tert-butylbenzaldehyde,11a 4-[(trimethyl-
silyl)ethynyl]benzaldehyde,11b 9,10-diiodoanthracene,16 1,4-dibro-
The compounds 1, 2, 14, 16, and 17 (Schemes 1 and 4)
correspond to different parts of the D-B-A systems. These
compounds have been used as references in the photo-
physical investigations.6 The bis(di-tert-butylphenyl)-
substituted porphyrins 1 (free base porphyrin) and 2 (zinc
porphyrin) have been used as model compounds for the
separate acceptor and donor, respectively. These porphy-
rins were isolated in the preparation of porphyrins 3 and
5. The bridge chromophores 1417 were prepared by Pd/Cu
catalyzed cross-coupling of phenylacetylene and 1,4-di-
19
monaphthalene,18 and Pd2(dba)3◊CHCl3 were prepared according
to the literature procedures.
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1158
J. Kajanus et al.
PAPER
with 10% aq Na2S2O3 solution (5 î 30 mL) and H2O (30 mL). The
organic phase was dried (Na2SO4), filtered, and evaporated. The
crude product was redissolved in CH2Cl2 (100 mL) and filtered
through a pad of silica. Removal of the solvent and recrystallization
from EtOH gave 2.42 g (61%) of pale yellow needles, mp 110–
111°C (Lit.21 mp 110–111°C).
N
N
N
N
Zn
7
1H NMR: d = 7.60 (AA’BB’, 2 H, ArH), 7.51 (s, 2 H, ArH), 8.04
(AA’BB’, 2 H, ArH).
a
13C NMR: d = 100.7, 128.6, 133.0, 134.7, 138.1.
5-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tet-
ramethyl-15-{4-[(trimethylsilyl)ethynyl]phenyl}porphyrin (5)
3,5-Di-tert-butylbenzaldehyde (1.10 g, 4.8 mmol), 4-[(trimethylsi-
lyl)ethynyl]benzaldehyde (0.97 g, 4.8 mmol) and 3,3’-diethyl-4,4’-
dimethyl-2,2’-dipyrrylmethane (2.10 g, 9.6 mmol) were dissolved
in anhyd MeCN (100 mL). Trichloroacetic acid (0.27 g, 1.6 mmol)
was added and the solution was stirred under argon at r.t. for 18 h in
the dark. A solution of DDQ (3.50 g, 15.4 mmol) in anhyd THF
(100 mL) was added, and the mixture was stirred for another 3 h. It
was then poured into H2O (200 mL) and extracted with CHCl3
(4 î 150 mL) until the extract was colorless. The combined CHCl3
layers were washed with 5% aq NaHCO3 solution (5 î 150 mL)
and H2O (150 mL), and dried (Na2SO4). Silica gel (20 g) was added
to the solution, the solvent was removed under reduced pressure,
and the sample was added to a chromatographic column. The por-
phyrins were separated by flash chromatography (silica gel, pen-
tane/Et2O, 40:1 to pentane/Et2O, 20:1). Recrystallization from
CH2Cl2/MeOH gave 1.32 g (33% yield; purple crystals) of 5 and
0.55 g (13% yield; purple crystals) of 1.22 The disilylated porphyrin
was not isolated.
N
N
N
N
Zn
R
12N 27 %
12A 48 %
b
95 %
N
HN
R
NH
N
13
c
I
N
R =
ZnP-NB-H2P (53 %)
ZnP-AB-H2P (48 %)
1H NMR: d = -2.44 (br s, 2 H, NH), 0.40 [s, 9 H, Si(CH3)3], 1.50
(s, 18 H, t-C4H9), 1.77 (m, 12 H, CH2CH3), 2.46 (s, 6 H, pyrrole-
CH3), 2.51 (s, 6 H, pyrrole-CH3), 4.02 (m, 8 H, CH2CH3), 7.80 (t, 1
H, J = 1.8 Hz, ArH), 7.88 (dm, 2 H, J = 8 Hz, ArH), 7.91 (d, 2 H,
J = 1.8 Hz, ArH), 8.05 (dm, 2 H, J = 8 Hz, ArH), 10.23 (s, 2 H, me-
so).
A
R =
I
HRMS: m/z Calcd for C57H70N4Si 838.537, found 838.536. m/z Cal-
cd for C57H70N4Si + H+ 839.545, found 839.545.
Scheme 3 Reagents and conditions: (a) diiodoaryl (5 equiv),
Pd2(dba)3◊CHCl3, Ph3As, toluene/Et3N (3:1), 40°C, 96 h; (b) TFA,
CH2Cl2, r.t., 1 h; (c) 7, Pd2(dba)3◊CHCl3, Ph3As, toluene/Et3N (3:1),
40°C, 48 h
Zinc(II) 5-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-
3,7,13,17-tetramethyl-15-{4-[(trimethylsilyl)ethynyl]phe-
nyl}porphyrin (6)
Free base porphyrin 5 (0.88 g, 1.05 mmol) was dissolved in CH2Cl2
(250 mL), then Zn(OAc)2◊2H20 (0.44 g, 2.0 mmol) dissolved in
MeOH (30 mL) was added. The mixture was stirred at r.t. for 3 h
and poured into EtOAc (200 mL). The solution was washed with
5% aq NaHCO3 solution (2 î 150 mL) and H2O (2 î 100 mL).
The organic phase was dried (Na2SO4), and evaporated. The residue
was redissolved in CH2Cl2 and chromatographed through a short
column of silica gel to remove free base porphyrin which was stuck
on the top of the column. Removal of the solvent gave 0.93 g (98%)
of a red powder.
1H NMR: d = 0.41 [s, 9 H, Si(CH3)3], 1.51 (s, 18 H, t-C4H9), 1.77
(m, 12 H, CH2CH3), 2.44 (s, 6 H, pyrrole-CH3), 2.49 (s, 6 H, pyr-
role-CH3), 4.01 (m, 8 H, CH2CH3), 7.81 (t, 1 H, J = 1.8 Hz, ArH),
7.87 (dm, 2 H, J = 8 Hz, ArH), 7.93 (d, 2 H, J = 1.8 Hz, ArH), 8.05
(dm, 2 H, J = 8 Hz, ArH), 10.19 (s, 2 H, meso).
Demetalation of Zinc Porphyrins; General Procedure
Zinc porphyrins were demetalated with trifluoroacetic acid (TFA)
using the method of Lindsey et al.20 The zinc porphyrin was dis-
solved in 10% TFA in CH2Cl2 (ca 0.5 mL/mmol) and the solution
immediately turned dark green. The mixture was stirred at r.t. for 1
h in the dark and poured into EtOAc. The solution was washed with
5% aq NaHCO3 solution until the reddish porphyrin color returned,
washed with H2O, and dried (Na2SO4). The free base porphyrins
were purified by chromatography on silica gel. Traces of zinc por-
phyrin were removed using CH2Cl2 and the free base porphyrin was
then eluted by adding MeOH to the eluent. Removal of the solvents
and drying in vacuo gave the free base porphyrins as brown solids
in 90–95% yield.
HRMS: m/z Calcd for C57H68N4SiZn 900.450, found 900.445.
1,4-Diiodonaphthalene
Zinc(II) 5-(3,5-Di-tert-butylphenyl)-15-(4-ethynylphenyl)-
2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin (7)
A sample of 6 (0.66 mmol, 0.60 g) was dissolved in anhyd THF
(100 mL) under argon. Bu4NF (1.3 mmol, 1.2 ml of a 1.1 M solution
in THF) was added, and the mixture was stirred at r.t. for 1 h. The
solvent was removed and the solid residue was dissolved in CHCl3
A solution of 1,4-dibromonaphthalene (3.00 g, 10.5 mmol) in anhyd
Et2O (40 mL) was treated with t-BuLi in pentane (53 mmol, 33 mL
of a 1.60 M solution) and iodine crystals (8.90 g, 35 mmol) using
the procedure of Duerr et al.16 The mixture was then diluted with
Et2O (100 mL) and transferred to a separatory funnel and washed
Synthesis 1999, No. 7, 1155–1162 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Bis(phenylethynyl)arylene-Linked Diporphyrins
1159
a
Diiodoaryl
R
R =
B
N
c
b
14
B 87 %
N 92 %
A 63 %
R
I
15
d
N
N
N
M
R
N
A
16 M = Zn
17 M = 2 H
e
Scheme 4 Reagents and conditions: (a) phenylacetylene, (Ph3)4Pd (5 mol%), CuI (10 mol%), Et3N, reflux, 2 h; (b) Ref. 17; (c) phenylacety-
lene, (Ph3P)4Pd (5 mol%), CuI (10 mol%), Et3N; (d) 7, Pd2(dba)3◊CHCl3, Ph3As, toluene/Et3N (3:1), reflux, 2 h; (e) TFA, CH2Cl2, r.t., 1 h
(150 mL). The organic phase was washed with 5% aq NaHCO3 so-
lution (2 ´ 50 mL), dried (Na2SO4), and filtered. Silica gel (15 g)
was added to the solution, the solvent was removed under reduced
pressure, and the sample was added to a chromatographic column.
Chromatography (silica gel , pentane/Et2O, 20:1) gave 0.47 g (86%)
of purple crystals.
1H NMR: d = 1.51 (s, 18 H, t-C4H9), 1.77 (m, 12 H, CH2CH3), 2.44
(s, 6 H, pyrrole-CH3), 2.47 (s, 6 H, pyrrole-CH3), 3.33 (s, 1 H,
CCH), 4.00 (m, 8 H, CH2CH3), 7.82 (t, 1 H, J = 1.8 Hz, ArH), 7.89
(dm, 2 H, J = 8 Hz, ArH), 7.94 (d, 2 H, J = 1.8 Hz, ArH), 8.06 (dm,
2 H, J = 8 Hz, ArH), 10.18 (s, 2 H, meso).
phyrinyl]phenylethynyl}benzene (10)
Ph3As (20 mg, 65 mmol) and Pd2(dba3)•CHCl3 (8 mg, 8 mmol) were
added to a deaerated solution of 3 (50 mg, 54 mmol) and the mono-
protected dialkyne 9 (23 mg, 81 mmol) in toluene/Et3N (3:1, 16 mL).
The mixture was stirred at 40°C for 4 h and concentrated. Chroma-
tography (silica gel, pentane/CH2Cl2, 3:1) and SEC gave 38 mg
(65%) of a red solid.
1H NMR: d = 1.17 [s, 21 H, CH(CH3)2], 1.51 (s, 18 H, t-C4H9), 1.77
(m, 12 H, CH2CH3), 2.45 (s, 6 H, pyrrole-CH3), 2.51 (s, 6 H, pyr-
role-CH3), 4.01 (m, 8 H, CH2CH3), 7.56 (dm, 2 H, J = 8 Hz, ArH),
7.64 (dm, 2 H, J = 8 Hz, ArH), 7.82 (t, 1 H, J = 1.8 Hz, ArH), 7.94
(m, 4 H, ArH), 8.10 (dm, 2 H, J = 8 Hz, ArH), 10.19 (s, 2 H, meso).
HRMS: m/z Calcd for C54H60N4Zn 828.411, found 828.409.
HRMS: m/z Calcd for C71H84N4SiZn 1084.594, found 1084.576.
Zinc(II) 5-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-
3,7,13,17-tetramethyl-15-iodophenylporphyrin (3)
Prepared from 4-iodobenzaldehyde (1.61 g, 6.94 mmol) as de-
scribed for 5. The crude porphyrin mixture was metalated as de-
scribed for 6 before separation on silica gel. Chromatography (silica
gel, pentane/CH2Cl2, 7:3) gave 1.62 g (25%) of 5 and 0.78 g (12%)
of 2.22
1H NMR: d = 1.51 (s, 18 H, t-C4H9), 1.77 (m, 12 H, CH2CH3), 2.44
(s, 6 H, pyrrole-CH3), 2.50 (s, 6 H, pyrrole-CH3), 4.00 (m, 8 H,
CH2CH3), 7.81 (t, 1 H, J = 1.8 Hz, ArH), 7.84 (dm, 2 H, J = 8 Hz,
ArH), 7.93 (d, 2 H, J = 1.8 Hz, ArH), 8.08 (dm, 2 H, J = 8 Hz,
ArH), 10.19 (s, 2 H, meso).
1-Ethynyl-4-{[zinc(II) porphyrinyl]phenylethynyl}benzene 11
The silylated ethynylporphyrin 10 (38 mg, 35 mmol) was deprotect-
ed with Bu4NF (105 mmol, 95 mL of a 1.1 M solution) using the
same procedure as in the preparation of 7. The crude product was
purified by SEC to remove residues of the protecting group. Re-
moval of the solvent and drying in vacuo afforded 24 mg (74%) of
11.
1H NMR: d = 1.51 (s, 18 H, t-C4H9), 1.77 (m, 12 H, CH2CH3), 2.44
(s, 6 H, pyrrole-CH3), 2.52 (s, 6 H, pyrrole-CH3), 3.22 (s, 1 H,
CCH), 4.01 (m, 8 H, CH2CH3), 7.57 (dm, 2 H, J = 8 Hz, ArH), 7.66
(dm, 2 H, J = 8 Hz, ArH), 7.82 (t, 1 H, J = 1.8 Hz, ArH), 7.93 (m,
4 H, ArH), 8.10 (dm, 2 H, J = 8 Hz, ArH), 10.19 (s, 2 H, meso).
HRMS: m/z Calcd for C52H59N4IZn 930.308, found 930.305.
5-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tet-
ramethyl-15-iodophenylporphyrin (4)
HRMS: m/z Calcd for C62H64N4Zn 928.442, found 928.445.
Zinc porphyrin 3 was demetalated as described above in the general
procedure.
1-{[5-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-
tetramethyl-15-porphyrinyl]phenylethynyl}-4-{[zinc(II) 5-(3,5-
di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-
15-porphyrinyl]phenylethynyl}benzene (ZnP-BB-H2P)
Ph3As (10 mg, 33 mmol) and Pd2(dba)3•CHCl3 (4 mg, 4 mmol) were
added to a deaerated solution of 4 (34 mg, 39 mmol) and zinc ethy-
nylporphyrin 11 (24 mg, 26 mmol) in toluene/Et3N (3:1, 12 mL).
The mixture was stirred at 40°C for 4 h and concentrated. Chroma-
tography (silica gel, CH2Cl2 to CH2Cl2/MeOH, 50:1), and SEC gave
27 mg (62%) of a red solid.
1H NMR: d = –2.44 (br s, 2 H, NH), 1.50 (s, 18 H, t-C4H9), 1.77 (m,
12 H, CH2CH3), 2.46 (s, 6 H, pyrrole-CH3), 2.53 (s, 6 H, pyrrole-
CH3), 4.02 (m, 8 H, CH2CH3), 7.81 (t, 1 H, J = 1.8 Hz, ArH), 7.84
(dm, 2 H, J = 8 Hz, ArH), 7.91 (d, 2 H, J = 1.8 Hz, ArH), 8.09 (dm,
2 H, J = 8 Hz, ArH), 10.23 (s, 2 H, meso).
HRMS: m/z Calcd for C52H61N4I 868.394, found 868.394. m/z Cal-
cd for C52H61N4I + H+ 869.402, found 869.402.
1H NMR: d = –2.41 (br s, 2 H, NH), 1.52 (s, 36 H, t-C4H9), 1.79 (m,
24 H, CH2CH3), 2.46 (s, 6 H, pyrrole-CH3), 2.47 (s, 6 H, pyrrole-
CH3), 2.56 (s, 6 H, pyrrole-CH3), 2.59 (s, 6 H, pyrrole-CH3), 4.03
1-[(Triisopropylsilyl)ethynyl]-4-{[zinc(II) 5-(3,5-di-tert-bu-
tylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-15-por-
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J. Kajanus et al.
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(m, 16 H, CH2CH3), 7.79 (s, 4 H, ArH), 7.82 (m, 2 H, ArH), 7.93 (d,
2 H, J = 1.8 Hz, ArH), 7.95 (d, 2 H, J = 1.8 Hz, ArH), 7.98 (dm, 4
H, J = 8 Hz, ArH), 8.14 (m, 4 H, ArH), 10.22 (s, 2 H, meso), 10.26
(s, 2 H, meso).
1-{[Free Base Porphyrinyl]phenylethynyl}-4-{[zinc(II) porphy-
rinyl]phenylethynyl}naphthalene ZnP-NB-H2P
Ph3As (9 mg, 29 mmol) and Pd2(dba)3◊CHCl3 (4 mg, 4 mmol) were
added to a deaerated solution of 13N (24 mg, 24 mmol) and 7 (30
mg, 36 mmol) in toluene/Et3N (3:1, 12 mL). The mixture was stirred
at 40°C for 4 d and concentrated. Chromatography (silica gel,
CH2Cl2 to CH2Cl2/MeOH, 50:1), and SEC gave 22 mg (53%) of a
red solid.
1H NMR: d = –2.38 (br s, 2 H, NH), 1.52 (s, 36 H, t-C4H9), 1.81 (m,
24 H, CH2CH3), 2.46 (s, 6 H, pyrrole-CH3), 2.48 (s, 6 H, pyrrole-
CH3), 2.61 (s, 6 H, pyrrole-CH3), 2.63 (s, 6 H, pyrrole-CH3), 4.05
(m, 16 H, CH2CH3), 7.82–7.88 (m, 4 H, ArH), 7.93 (d, 2 H, J = 1.8
Hz, ArH), 7.95 (d, 2 H, J = 1.8 Hz, ArH), 8.03 (s, 2 H, ArH), 8.11
(dm, 4 H, J = 8 Hz, ArH), 8.20 (m, 4 H, ArH), 8.79 (AA’BB’, 2 H,
ArH), 10.23 (s, 2 H, meso), 10.27 (s, 2 H, meso).
HRMS: m/z Calcd for C114H124N8Zn 1668.924, found 1668.936.
1-Iodo-4-{[zinc(II) 5-(3,5-di-tert-butylphenyl)-2,8,12,18-tetra-
ethyl-3,7,13,17-tetramethyl-15-porphyrinyl]phenylethy-
nyl}naphthalene (12N)
Ph3As (32 mg, 106 mmol) and Pd2(dba)3◊CHCl3 (13 mg, 13 mmol)
were added to a deaerated solution of 7 (73 mg, 88 mmol) and 1,4-
diiodonaphthalene (167 mg, 440 mmol) in toluene/Et3N (3:1, 28
mL). The mixture was stirred at 40°C for 4 days and concentrated.
Chromatography (silica gel, pentane/CH2Cl2, 3:1) gave 26 mg
(27%) of a red solid.
1H NMR: d = 1.52 (s, 18 H, t-C4H9), 1.78 (m, 12 H, CH2CH3), 2.45
(s, 6 H, pyrrole-CH3), 2.56 (s, 6 H, pyrrole-CH3), 4.02 (m, 8 H,
CH2CH3), 7.61 (d, 1 H, J = 7.6 Hz, ArH), 7.66 (AA’BB’, 1 H,
ArH), 7.73 (AA’BB’, 1 H, ArH), 7.82 (t, 1 H, J = 1.8 Hz, ArH),
7.94 (d, 2 H, J = 1.8 Hz, ArH), 8.05 (dm, 2 H, J = 8.0 Hz, ArH),
8.16 (m, 4 H, ArH), 8.62 (AA’BB’, 1 H, ArH), 10.20 (s, 2 H, meso).
HRMS: m/z Calcd for C118H126N8Zn 1718.940, found 1718.849.
9-{[Free Base Porphyrinyl]phenylethynyl}-10-{[zinc(II) por-
phyrinyl]phenylethynyl}anthracene ZnP-AB-H2P
Prepared from 13A (35 mg, 33 mmol) and 7 (39 mg, 47 mmol) as de-
scribed for ZnP-NB-H2P. Chromatography (silica gel, CH2Cl2 to
CH2Cl2/MeOH, 50:1), and SEC gave 28 mg (48%) of a red solid.
1H NMR: d = –2.38 (br s, 2 H, NH), 1.52 (s, 36 H, t-C4H9), 1.81 (m,
24 H, CH2CH3), 2.46 (s, 6 H, pyrrole-CH3), 2.48 (s, 6 H, pyrrole-
CH3), 2.65 (s, 6 H, pyrrole-CH3), 2.67 (s, 6 H, pyrrole-CH3), 4.05
(m, 16 H, CH2CH3), 7.83 (m, 6 H, ArH), 7.93 (d, 2 H, J = 1.8 Hz,
ArH), 7.95 (d, 2 H, J = 1.8 Hz, ArH), 8.25 (s, 8 H, ArH), 9.02
(AA’BB’, 4 H, ArH), 10.24 (s, 2 H, meso), 10.28 (s, 2 H, meso).
HRMS: m/z Calcd for C64H65IN4Zn 1080.355, found 1080.367.
9-Iodo-10-{[zinc(II) porphyrinyl]phenylethynyl}anthracene
12A
Prepared from zinc ethynylporphyrin 7 (95 mg, 0.11 mmol) and
9,10-diiodoanthracene (237 mg, 0.55 mmol) as described for 12N.
Following purification by column chromatography (silica gel, pen-
tane/CH2Cl2, 4:1 to pentane/CH2Cl2, 2:1) and SEC, 12A was isolat-
ed in 48% yield.
1H NMR: d = 1.52 (s, 18 H, t-C4H9), 1.78 (m, 12 H, CH2CH3), 2.45
(s, 6 H, pyrrole-CH3), 2.61 (s, 6 H, pyrrole-CH3), 4.02 (m, 8 H,
CH2CH3), 7.63 (AA’BB’, 2 H, ArH), 7.69 (AA’BB’, 2 H, ArH),
7.82 (t, 1 H, J = 1.8 Hz, ArH), 7.94 (d, 2 H, J = 1.8 Hz, ArH), 8.21
(m, 4 H, ArH), 8.54 (AA’BB’, 2 H, ArH), 8.88 (AA’BB’, 2 H,
ArH), 10.19 (s, 2 H, meso).
HRMS: m/z Calcd for C122H128N8Zn 1768.955, found 1768.930.
1-Phenylethynyl-4-iodobenzene (15B)
Phenylacetylene (0.22 mL, 2.0 mmol) was added to a deaerated so-
lution of 1,4-diiodobenzene (2.0 g, 6.1 mmol), (Ph3P)4Pd (48 mg, 41
mmol) and CuI (16 mg, 84 mmol) in Et3N (40 mL). The mixture was
stirred at r.t. for 1.5 h, filtered, and evaporated. Flash chromatogra-
phy (silica gel, pentane/toluene, 100:1) gave 0.48 g (78%) of a white
powder. Recrystallization from EtOH gave white flakes, mp 105–
106 °C (Lit.17a mp 103–105 °C).
HRMS: m/z Calcd for C68H67IN4Zn 1130.370, found 1130.365.
1H NMR: d = 7.25 (dm, 2 H, J = 8 Hz, ArH), 7.35 (m, 3 H, ArH),
7.52 (m, 2 H, ArH), 7.69 (dm, 2 H, J = 8 Hz, ArH).
Free Base Iodoporphyrins 13
The zinc iodoporphyrins 12 were demetalated as described above in
the general procedure.
1-Phenylethynyl-4-iodonaphthalene (15N)
Prepared from 1,4-diiodonaphthalene (0.95 g, 2.5 mmol) as de-
scribed for 15B. The mixture was stirred at r.t. for 30 min and then
heated to reflux for another 30 min. The mixture was cooled, fil-
tered, and evaporated. Column chromatography (silica gel, pentane/
toluene, 40:1) gave 211 mg (72%) of a colorless oil which solidi-
fied. Recrystallization from EtOH gave white needles, mp 90–
91°C.
1H NMR: d = 7.40 (m, 3 H, ArH), 7.45 (d, 1 H, J = 8 Hz, ArH), 7.64
(m, 4 H, ArH), 8.08 (d, 1 H, J = 8 Hz, ArH), 8.12 (AA’BB’, 1 H,
ArH), 8.40 (AA’BB’, 1 H, ArH).
Compound 13N
1H NMR: d = –2.41 (br s, 2 H, NH), 1.51 (s, 18 H, t-C4H9), 1.79 (m,
12 H, CH2CH3), 2.47 (s, 6 H, pyrrole-CH3), 2.59 (s, 6 H, pyrrole-
CH3), 4.03 (m, 8 H, CH2CH3), 7.63 (d, 1 H, J = 7.6 Hz, ArH), 7.70
(AA’BB’, 1 H, ArH), 7.78 (AA’BB’, 1 H, ArH), 7.81 (t, 1 H,
J = 1.8 Hz, ArH), 7.92 (d, 2 H, J = 1.8 Hz, ArH), 8.05 (dm, 2 H,
J = 8.0 Hz, ArH), 8.14–8.22 (m, 4 H, ArH), 8.63 (AA’BB’, 1 H,
ArH), 10.25 (s, 2 H, meso).
HRMS: m/z Calcd for C64H67IN4 1018.441, found 1018.440. Calcd
for C64H67IN4+H+1019.449, found 1019.446.
HRMS: m/z Calcd for C18H11I 353.991, found 353.995.
Compound 13A
Anal. Calcd for C18H11I: C, 61.04; H, 3.13. Found C, 60.97; H, 3.04.
1H NMR: d = –2.40 (br s, 2 H, NH), 1.51 (s, 18 H, t-C4H9), 1.80 (m,
12 H, CH2CH3), 2.47 (s, 6 H, pyrrole-CH3), 2.64 (s, 6 H, pyrrole-
CH3), 4.04 (m, 8 H, CH2CH3), 7.72 (AA’BB’, 4 H, ArH), 7.81 (t, 1
H, J = 1.8 Hz, ArH), 7.93 (d, 2 H, J = 1.8 Hz, ArH), 8.20 (m, 4 H,
ArH), 8.60 (AA’BB’, 2 H, ArH), 8.91 (AA’BB’, 2 H, ArH), 10.26
(s, 2 H, meso).
9-Phenylethynyl-10-iodoanthracene (15A)
Prepared from 9,10-diiodoanthracene (0.86 g, 2.0 mmol) using the
same procedure as for the preparation of 13A. The mixture was fil-
tered and the solids were washed with a small amount of toluene,
leaving most of the unreacted diiodoanthracene on the filter. The fil-
trate was evoporated. The residue was dissolved in toluene, silica
gel (5 g) was added, the solvent removed under reduced pressure,
and the sample added to a chromatographic column. Column chro-
matography (silica gel, pentane/toluene, 40:1) gave 90 mg (33%
yield) of a yellow solid, mp 165–166°C.
HRMS: m/z Calcd for C68H69IN4 1068.457, found 1068.463. m/z
Calcd for C68H69IN4 + H+1069.465, found 1069.474.
Synthesis 1999, No. 7, 1155–1162 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Bis(phenylethynyl)arylene-Linked Diporphyrins
1161
1H NMR: d = 7.45 (m, 3 H, ArH) 7.62 (AA’BB’, 4 H, ArH), 7.78
(m, 2 H, ArH), 8.52 (AA’BB’, 2 H, ArH), 8.66 (AA’BB’, 2 H,
ArH).
H, ArH), 7.81 (t, 1 H, J = 1.8 Hz, ArH), 7.84 (d, 1 H, J = 8 Hz,
ArH), 7.92 (m, 3 H, ArH), 8.07 (dm, 2 H, J = 8 Hz, ArH), 8.16 (dm,
2 H, J = 8 Hz, ArH), 8.56 (AA’BB’, 1 H, ArH), 8.71 (AA’BB’, 1 H,
ArH), 10.25 (s, 2 H, meso).
FAB-MS: m/z Calcd for C72H72N4 + H+ 993.6, found 993.2.
HRMS: m/z Calcd for C22H13I 404.006, found 404.008.
Anal. Calcd for C22H13I: C, 65.37; H, 3.24. Found C, 65.49; H, 3.22.
Compound 17A
1H NMR: d = –2.40 (br s, 2 H, NH), 1.51 (s, 18 H, t-C4H9), 1.79 (m,
12 H, CH2CH3), 2.47 (s, 6 H, pyrrole-CH3), 2.64 (s, 6 H, pyrrole-
CH3), 4.05 (m, 8 H, CH2CH3), 7.49 (m, 3 H, ArH), 7.68–7.85 (m, 7
H, ArH), 7.93 (d, 2 H, J = 1.8 Hz, ArH), 8.21 (m, 4 H, ArH), 8.78
(AA’BB’, 2 H, ArH), 8.94 (AA’BB’, 2 H, ArH), 10.26 (s, 2 H, me-
so).
1-Phenylethynyl-4-{[zinc(II) 5-(3,5-di-tert-butylphenyl)-
2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-15-porphyrinyl]phe-
nylethynyl}benzene (ZnP-phenylene-Bridged 16B)
To a deaerated solution of 7 (58 mg, 70 mmol) and 15B (43 mg, 141
mmol) in toluene/Et3N (3:1, 12 mL) were added Pd2(dba)3◊CHCl3
(11 mg, 11 mmol) and Ph3P (22 mg, 84 mmol) under argon flushing.
The mixture was refluxed for 2 h, cooled and concentrated. Chro-
matography (silica gel, hexane/CH2Cl2, 2:1), and SEC gave 42 mg
(60%) of a red solid.
FAB-MS: m/z Calcd for C76H74N4 + H+ 1043.6, found 1043.3.
1H NMR: d = 1.51 (s, 18 H, t-C4H9), 1.78 (m, 12 H, CH2CH3), 2.45
(s, 6 H, pyrrole-CH3), 2.52 (s, 6 H, pyrrole-CH3), 4.01 (m, 8 H,
CH2CH3), 7.38 (m, 3 H, ArH), 7.58 (m, 2 H, ArH), 7.61 (dm, 2 H,
J = 8 Hz, ArH), 7.69 (dm, 2 H, J = 8 Hz, ArH), 7.82 (t, 1 H, J = 1.8
Hz, ArH), 7.94 (m, 4 H, ArH), 8.11 (dm, 2 H, J = 8 Hz, ArH), 10.20
(s, 2 H, meso).
Acknowledgement
We thank Dr. Gunnar Stenhagen, Department of Organic Chemi-
stry, Chalmers University of Technology, for performing the mass
spectrometry measurements. We also like to thank M Sc. Anh Tran
and M Sc. Adam Hurynowicz. Financial support from the Swedish
Natural Science Research Council, the Swedish Research Council
for Engineering Sciences and the Carl Trygger Foundation is grate-
fully acknowledged.
HRMS: m/z Calcd for C68H68N4Zn 1004.474, found 1004.473.
1-Phenylethynyl-4-{[zinc(II) porphyrinyl]phenylethynyl}naph-
thalene, ZnP-naphthylene-Bridged 16N
Prepared from 7 (73 mg, 88 mmol) and 15N (62 mg, 176 mmol) as
described for 16B. Chromatography (silica gel, hexane/CH2Cl2,
2:1) and SEC gave 63 mg (68% yield) of a red solid.
1H NMR: d = 1.52 (s, 18 H, t-C4H9), 1.78 (m, 12 H, CH2CH3), 2.46
(s, 6 H, pyrrole-CH3), 2.55 (s, 6 H, pyrrole-CH3), 4.01 (m, 8 H,
CH2CH3), 7.42 (m, 3 H, ArH), 7.68–7.84 (m, 6 H, ArH), 7.91 (d, 1
H, J = 8 Hz, ArH), 7.95 (d, 2 H, J = 1.8 Hz, ArH), 8.06 (dm, 2 H,
J = 8 Hz, ArH), 8.15 (dm, 2 H, J = 8 Hz, ArH), 8.53 (AA’BB’, 1 H,
ArH), 8.70 (AA’BB’, 1 H, ArH), 10.19 (s, 2 H, meso).
References
(1) Newton, M. D. Chem. Rev. 1991, 91, 767.
(2) Antennas and Reaction Centers in Photosynthetic Bacteria;
Michel-Beyerly, M. E., Ed.; Springer Verlag: New York,
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(3) (a) Wagner, R. W.; Lindsey, J. S.; Seth, J.; Palaniappan, V.;
Bocian, D. F. J. Am. Chem. Soc. 1996, 118, 3996.
(b) Balzani, V; Scandola, F. Supramolecular Chemistry, Ellis
Horwood: Chichester, UK, 1991, Chap. 12.
(4) (a) Vollmer, M. S.; Würthner, F.; Effenberger F.; Emele, P.;
Meyer, D. U.; Stümpfig, T.; Port, H.; Wolf, H.C. Chem. Eur.
J. 1998, 4, 260.
HRMS: m/z Calcd for C72H70N4Zn 1054.489, found 1054.508.
9-Phenylethynyl-10-{[zinc(II) porphyrinyl]phenylethynyl}an-
thracene, ZnP-anthrylene-Bridged 16A
Prepared from 7 (30 mg, 36 mmol) and 15A (32 mg, 79 mmol) as de-
scribed for 16B. Chromatography (silica gel, hexane/CH2Cl2, 2:1)
and SEC gave 26 mg (65%) of a red solid.
(b) Strachan, J. P.; Gentemann, S.; Seth, J.; Kalsbeck, W. A.;
Lindsey, J. S.; Holten, D.; Bocian, D. F. J. Am. Chem. Soc.
1997, 119, 11191.
1H NMR: d = 1.52 (s, 18 H, t-C4H9), 1.79 (m, 12 H, CH2CH3), 2.46
(s, 6 H, pyrrole-CH3), 2.62 (s, 6 H, pyrrole-CH3), 4.03 (m, 8 H,
CH2CH3), 7.49 (m, 3 H, ArH), 7.75 (AA’BB’, 4 H, ArH), 7.82 (m,
3 H, ArH), 7.95 (d, 1 H, J = 8 Hz, ArH), 8.21 (m, 4 H, ArH), 8.77
(AA’BB’, 2 H, ArH), 8.94 (AA’BB’, 2 H, ArH), 10.22 (s, 2 H, me-
so).
(c) Grosshenny, V.; Harriman, A.; Ziessel, R. Angew.
Chem.1995, 107, 1211; Angew. Chem. Int. Ed. Engl. 1995, 34,
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(d) Barigelletti, F.; Flamigni, L.; Balzani, V.; Collin, J.-P.;
Sauvage, J.-P; Sour, A.; Constable, E. C.; Cargill Thompson,
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3590.
HRMS: m/z Calcd for C76H72N4Zn 1104.505, found 1104.509.
H2P-Arylene-Bridged 17
The zinc porphyrins 16 were demetalated as described above.
Compound 17B
1H NMR: d = –2.43 (br s, 2 H, NH), 1.51 (s, 18 H, t-C4H9), 1.78 (m,
12 H, CH2CH3), 2.46 (s, 6 H, pyrrole-CH3), 2.56 (s, 6 H, pyrrole-
CH3), 4.03 (m, 8 H, CH2CH3), 7.38 (m, 3 H, ArH), 7.58 (m, 2 H,
ArH), 7.61 (dm, 2 H, J = 8 Hz, ArH), 7.69 (dm, 2 H, J = 8 Hz,
ArH), 7.81 (t, 1 H, J = 1.8 Hz, ArH), 7.92 (d, 2 H, J = 1.8 Hz, ArH),
7.94 (dm, 2 H, J = 8 Hz, ArH), 8.11 (dm, 2 H, J = 8 Hz, ArH), 10.24
(s, 2 H, meso).
(5) (a) Kawabata, S.; Yamazaki, I.; Nishimura, Y.; Osuka, A. J.
Chem. Soc., Perkin Trans. 2 1997, 479.
(b) Strachan, J.-P.; Gentemann, S.; Seth, J.; Kalsbeck, W. A.;
Lindsey, J. S.; Holten, D.; Bocian, D. F. J. Am. Chem. Soc.
1997, 119, 11191.
(c) Wagner, R. W.; Johnson, T. E.; Lindsey, J. S. J. Am. Chem.
Soc. 1996, 118, 11166.
(d) Hsiao, J.-S.; Krueger, B. P.; Wagner, R. W.; Johnson, T.
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J. S.; Bocian, D. F.; Donohoe, R. J. J. Am. Chem. Soc. 1996,
118, 11181.
FAB-MS: m/z Calcd for C68H70N4 + H+ 943.6, found 943.2.
Compound 17N
1H NMR: d = –2.41 (br s, 2 H, NH), 1.51 (s, 18 H, t-C4H9), 1.79 (m,
12 H, CH2CH3), 2.47 (s, 6 H, pyrrole-CH3), 2.60 (s, 6 H, pyrrole-
CH3), 4.04 (m, 8 H, CH2CH3), 7.43 (m, 3 H, ArH), 7.68–7.80 (m, 4
Synthesis 1999, No. 7, 1155–1162 ISSN 0039-7881 © Thieme Stuttgart · New York

1162
J. Kajanus et al.
PAPER
(e) Seth, J.; Palaniappan, V.; Wagner, R. W.; Johnson, T. E.;
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Article Identifier:
1437-210X,E;1999,0,07,1155,1162,ftx,en;H11398SS.pdf
Synthesis 1999, No. 7, 1155–1162 ISSN 0039-7881 © Thieme Stuttgart · New York