Practical synthesis of perylene-monoimide building blocks that possess features appropriate for use in porphyrin-based light-harvesting arrays

Article abstract of DOI:10.1016/S0040-4020(03)00020-6

Perylene-monoimide dyes with solubilizing aryloxy substituents at the perylene perimeter and a synthetic handle on the N-aryl group are valuable building blocks for incorporation as accessory pigments in porphyrin-based light-harvesting arrays. A family of such dyes has been prepared by reaction of 1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboxylic anhydride with a set of 4-iodo/ethynyl anilines (with or without 2,6-diisopropyl substituents) in the presence of Zn(OAc)₂·2H₂O in imidazole/mesitylene at 130°C. The workup procedures throughout the synthesis have been streamlined for scale-up purposes, minimizing chromatography. Two bis(perylene)porphyrin building blocks were prepared in a rational manner and examined in Sonogashira and Glaser polymerizations. The two isopropyl groups on the N-aryl group and the three 4-tert-butylphenoxy groups at the perylene perimeter are essential for high solubility of the bis(perylene)porphyrins and corresponding oligomers in organic solvents.

Full text of DOI:10.1016/S0040-4020(03)00020-6

Tetrahedron 59 (2003) 1191–1207
Practical synthesis of perylene-monoimide building blocks
that possess features appropriate for use in porphyrin-based
light-harvesting arrays
*
Kin-ya Tomizaki, Patchanita Thamyongkit, Robert S. Loewe and Jonathan S. Lindsey
Department of Chemistry, North Carolina State University, Campus Box 8204, Raleigh, NC 27695-8204, USA
Received 11 November 2002; revised 30 December 2002; accepted 30 December 2002
Abstract—Perylene-monoimide dyes with solubilizing aryloxy substituents at the perylene perimeter and a synthetic handle on the N-aryl
group are valuable building blocks for incorporation as accessory pigments in porphyrin-based light-harvesting arrays. A family of such dyes
has been prepared by reaction of 1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboxylic anhydride with a set of 4-iodo/ethynyl anilines
(with or without 2,6-diisopropyl substituents) in the presence of Zn(OAc)2·2H2O in imidazole/mesitylene at 1308C. The workup procedures
throughout the synthesis have been streamlined for scale-up purposes, minimizing chromatography. Two bis(perylene)porphyrin building
blocks were prepared in a rational manner and examined in Sonogashira and Glaser polymerizations. The two isopropyl groups on the N-aryl
group and the three 4-tert-butylphenoxy groups at the perylene perimeter are essential for high solubility of the bis(perylene)porphyrins and
corresponding oligomers in organic solvents. q 2003 Elsevier Science Ltd. All rights reserved.
1. Introduction
light-harvesting studies, we have prepared several perylene-
monoimide–porphyrin dyads,5–7 a linear array of one
perylene-monoimide and two or four porphyrins,19 con-
structs with multiple perylene-monoimides surrounding
one porphyrin,20 and rod-like oligomers comprised of a
porphyrin-based backbone with two or four perylene-
monoimide dyes per porphyrin.21
Perylene dyes have found widespread applications ranging
from industrial pigments to components of molecular
photonic devices.1,2 In most cases, perylene-bis(imide)
dyes (e.g. 1) have been employed rather than perylene-
monoimide dyes (e.g. 2) (Chart 1). Both types of perylene-
imide dyes have optical features that make them
candidates for use as accessory pigments in conjunction
with porphyrins. However, perylene-bis(imide) dyes easily
undergo photo-induced reduction, an undesired process in
light-harvesting arrays.2–4 Perylene-monoimide dyes are
more resistant toward reduction than perylene-bis(imide)
dyes,5–8 making the former quite attractive for use in light-
harvesting applications.
The synthetic chemistry of perylene-monoimide dyes has
developed rapidly over the past few years. Langhals
developed a method for converting the commercially
available perylene-dianhydride 3 into perylene-monoimide
2,9 which provides the starting point in most routes
to substituted perylene-monoimide dyes. Mu¨llen has
developed methods for halogenation and substitution of
perylene-monoimide dyes10–12 and has incorporated peryl-
ene-monoimide dyes in dendrimeric architectures.13
Wasielewski has developed a variety of perylene-mono-
imide dyes for use in molecular photonic switches.14–18 For
Keywords: perylene; perylene anhydride; perylene imide; imidation;
porphyrin; light harvesting; accessory pigment.
*
Corresponding author. Tel.: þ1-919-515-6406; fax: þ1-919-513-2830;
e-mail: jlindsey@ncsu.edu
Chart 1.
0040–4020/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0040-4020(03)00020-6

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K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
Chart 2.
A chief challenge in working with perylene-imide dyes is to
overcome their intrinsically low solubility. A widespread
approach with perylene-bis(imide) dyes has been to
incorporate 2,5-di-tert-butyl22,23 or 2,6-diisopropyl10,24
substituents on aryl groups located at the N-imide positions.
The absorption and emission characteristics of perylene-
imide dyes are little affected by the presence of solubilizing
substituents at the imide positions because of the nodes
present at the imide nitrogen in both the HOMO and
LUMO.25 The same tactic of using alkylated N-aryl groups
has been carried over to the perylene-monoimide dyes, but
additional solubilizing features also have been sought by
introducing aryloxy substituents at the perimeter of the
perylene.10,11 The aryloxy substituents cause a batho-
chromic shift of the absorption and emission spectra and
alter the electrochemical properties as well. After extensive
studies of perylene–porphyrin dyads,3–7 we found that the
perylene-monoimide of choice for use with a porphyrin in a
light-harvesting array has three aryloxy substituents (1, 6,
and 9-positions) and a synthetic handle located on the N-aryl
group (4, Chart 2). The use of three aryloxy groups affords
a more soluble perylene dye than that substituted with one
9-aryloxy group (5).20
The synthetic strategy we employed to gain access to 4 is
shown in Scheme 1.7 The perylene-dianhydride 3 undergoes
imidation and double decarboxylation upon reaction with
the aniline bearing the desired synthetic handle, in this case
4-bromo-2,6-diisopropylaniline, forming perylene-mono-
imide 6. Bromination of 6 affords the tetrabromo derivative
7, which undergoes regioselective aryloxylation to give the
tris(aryloxy)perylene-monoimide 8 bearing the p-bromo
substituent on the aryl group at the N-imide position. Direct
coupling of 8 in dilute solution with ethynyl-porphyrins
proceeded very poorly. However, ethynylation with (tri-
methylsilyl)acetylene followed by deprotection provided
access to a perylene-monoimide building block (4) that
could be used in dilute-solution couplings.
Scheme 1.
There were two limitations in the synthetic approach
outlined in Scheme 1. Strategically, the synthetic handle is
introduced in the first step upon reaction with 3. With this
approach, the synthesis of other perylene-monoimides
bearing different synthetic handles requires the entire
synthesis to be performed. Practically, the yields in the
synthesis were generally acceptable, but a number of

K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1193
Chart 3.
reactions employed extensive chromatography and mul-
tiple aqueous/organic extraction schemes for purification.
Perylene-monoimide dyes typically can be readily precipi-
tated but crystallize poorly. Thus, motivated by issues of
strategy and practicality, we have worked to develop a new
synthesis that provides access to a family of perylene-
monoimide dyes without laborious chromatography.
Our results are presented in three parts. In Part 1, we
describe the synthesis of a perylene-anhydride (9, Chart 3)
that can be used in reactions with a variety of substituted
anilines, thereby affording the corresponding perylene-
monoimide dyes. The syntheses employ procedures in lieu
of column chromatography that are rapid and amenable
to scale up, including precipitation, trituration, filtration,
vacuum filtration over short silica pads, and occasional use
of aqueous/organic extractions. In Part 2, we employ several
of the perylene-monoimide dyes in the synthesis of
perylene–porphyrin building blocks. In Part 3, we investi-
gate the preparation of several perylene–porphyrin arrays
using the new perylene-monoimide dyes. One issue we have
explored concerns the necessity of the solubilizing 2,6-di-
isopropyl groups on the aryl group at the N-imide position
given the presence of aryloxy groups around the perimeter
of the perylene, particularly when such dyes are incorpo-
rated in perylene–porphyrin arrays. Taken together, the
approaches described herein should provide streamlined
access to a variety of soluble perylene-monoimide dyes for
use as building blocks in materials chemistry applications.
2. Results and discussion
2.1. Synthesis of perylene-monoimide building blocks
Perylene-3,4:9,10-tetracarboxylic dianhydride (3) is avail-
able commercially in large quantities and has been used as
the starting point in the synthesis of the monoimide 2.9 The
latter has been used to prepare the tribromo monoimide
10,10,14,15 a versatile intermediate in the synthesis of peryl-
ene-monoimide dyes.14–18 The synthesis of 2 employed
extensive extraction followed by column chromatography,
while the synthesis of 10 relied heavily on column
chromatography. We followed the literature procedures
for preparing 2 and 10 but modified the workup procedures.
Scheme 2.
Thus, treatment of 3 with 2,5-di-tert-butylaniline in the
presence of Zn(OAc)2·2H2O in H2O and imidazole at 1908C
in an autoclave afforded a mixture of the perylene-
bis(imide) 1 and the desired perylene-monoimide 2
(Scheme 2). The crude product was precipitated by addition
of water, collected by filtration, and dried. A solution of
the crude material was vacuum filtered through a pad of

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K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
essential for being able to purify the subsequent imidation
product.
Perylene-anhydride 9 should be a versatile intermediate for
preparing diverse perylene-monoimide dyes. Langhals has
shown that perylene-3,4-dicarboxylic anhydrides undergo
imidation with a variety of amines,9 and Wasielewski has
shown that related perylene-anhydrides undergo imidation
with hydrazine14,15 or a 4-(5-porphinyl)aniline.17 We sought
to condense 9 with several aniline derivatives, including
4-ethynylaniline (12a), 2,6-diisopropylaniline (12b), 4-iodo-
2,6-diisopropylaniline (12c), and a 2,6-diisopropylaniline
bearing an ethynyl group at the 4-position. For the latter, we
examined 2,6-diisopropyl-4-[2-(triisopropylsilyl)ethynyl]-
aniline (12d), 2,6-diisopropyl-4-[2-(trimethylsilyl)ethynyl]-
aniline (12e), and 2,6-diisopropyl-4-ethynylaniline (12f).
Anilines 12a and 12b are commercially available while 12c
is a known compound.26 Sonogashira coupling of 12c and
(triisopropylsilyl)acetylene or (trimethylsilyl)acetylene
afforded the corresponding aniline 12d or 12e in 88 or
86% yield, respectively (Scheme 3). Deprotection of 12e
with tetrabutylammonium fluoride (TBAF) on silica gel in
THF at room temperature furnished 12f in 61% yield. All
aniline derivatives were purified by vacuum filtration
through a pad of silica, affording analytically pure
compounds.
Scheme 3.
silica, enabling removal of a small amount of perylene
formed by exhaustive decarboxylation. The filtrate
(CH2Cl2) contained the bis(imide) 1 and the monoimide 2.
Addition of methanol gave some selectivity in precipitation,
affording 2 in ,90% purity (49% estimated yield) with the
remaining ,10% consisting of 1. While repeated fractional
precipitation could afford a more pure product, the crude
material was used directly in the bromination process
because the bis(imide) 1 is more polar than 2 and can easily
be removed in the workup of the tribrominated product 10.
The methods for imidation of perylene-anhydrides include
reaction in the presence of zinc acetate in solvents such as
molten imidazole,9 pyridine,23 or quinoline23 at reflux.
Similar imidations have been performed in DMF alone.15
The reaction of perylene-anhydride 9 with 3 equiv. of
4-ethynylaniline (12a) was performed in the presence of
Zn(OAc)2·2H2O in anhydrous DMF for 17 h (entry 1 in
Table 1; Scheme 4). The addition of water yielded a
precipitate consisting of the desired ethynyl-perylene (13a)
as the dominant product, a small amount of perylene starting
material, an unknown byproduct, and 12a. TLC analysis
showed the first three components to have similar polarities.
The precipitate was washed with aqueous methanol to
remove unreacted 12a. The precipitate was dissolved and
vacuum filtered through a pad of silica, affording a filtrate
containing relatively pure ethynyl-perylene. The filtrate was
evaporated and triturated with methanol to afford 13a in
50% yield. Anhydride 9 was also treated with 3 equiv. of
4-ethynylaniline (12a) in the presence of Zn(OAc)2·2H2O in
molten imidazole and mesitylene, affording 13a in 64%
yield (entry 2). The use of molten imidazole for the
imidation of perylene-anhydride 9 gave higher yield and a
shorter reaction time compared with the reaction in DMF.
The crude sample of 2 was treated with excess Br2 in CHCl3
under reflux. TLC analysis showed two major products of
nearly equal intensity with similar Rf values and a minor,
more polar component. Vacuum filtration through a pad of
silica yielded a filtrate containing compound 10 in ,90%
purity. Evaporation of the filtrate, partial dissolution in
CH2Cl2, and addition of hexanes yielded pure 10 as a solid
in 32% yield that was collected by filtration.
Compound 10 was treated with 4-tert-butylphenol and
K2CO3 in anhydrous DMF under reflux. (The reaction at
lower temperature affords the 1,6-diaryloxy-9-bromo
derivative.10,14,15) The addition of water followed by
filtration afforded 11 and a major byproduct. Dissolution
of the filtered material and vacuum filtration through a pad
of silica gave the filtrate containing pure 11 in 54% yield.
The conversion of the imide to the anhydride proceeds
through a base-mediated hydrolysis yielding the dicarb-
oxylate intermediate, which subsequently undergoes acid-
mediated dehydration.9 Compound 11 was refluxed in the
presence of KOH in 2-methyl-2-propanol followed by
treatment with acetic acid. The addition of water yielded the
anhydride as the dominant product and small amounts of a
non-polar product (likely 11) and a very polar byproduct
(presumably the diacid). The crude material was dissolved
and vacuum filtered through a pad of silica, yielding a
filtrate containing the anhydride 9 and a trace amount of the
polar byproduct. Evaporation to dryness, trituration with a
small amount of methanol, and filtration afforded pure 9 in
63% yield. Removal of both impurities at this stage is
The reaction of perylene-anhydride 9 with 12a affords the
ethynyl perylene-monoimide dye lacking isopropyl groups.
The reaction of 9 with 2,6-diisopropyl-substituted anilines is
expected to be more demanding owing to the steric
hindrance of the amine. We employed the imidation of 9
with 2,6-diisopropylaniline (12b) affording perylene-mono-
imide 13b as a benchmark for developing suitable reaction
conditions for sterically hindered amines. The reaction in
the presence of Zn(OAc)2·2H2O in DMF, pyridine, quino-
line, or ethylene glycol resulted in recovery of the starting
material. By the use of molten imidazole with mesitylene as
a fluid cosolvent, the difficulties in the imidation with the

K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1195
Table 1. Imidation of 9 with aniline derivatives
Entry
Product
Aniline (equiv.)
Solvent
Time (h)
Yield (%)
1a
2
3
4
5
6
7a
13a
13a
13b
13b
13c
4
12a (3)
12a (3)
12b (3)
12b (20)
12c (3)
12f (3)
DMF
17
2
50
64
35
40
30
Imidazole/mesitylene
Imidazole/mesitylene
Imidazole/mesitylene
Imidazole/mesitylene
Imidazole/mesitylene
Imidazole/mesitylene
20
24
23
24
36
b
–
48
13d
12d (20)
Imidation was carried out at 1308C in the presence of Zn(OAc)2·2H2O.
Preparative scale.
a
b
Starting material and/or product decomposed.
sterically hindered aniline were partly overcome, affording
a 35% yield of 13b (entry 3). An increase in the amount of
2,6-diisopropylaniline (,20 equiv.) gave a yield of 40%
(entry 4). The synthesis of 13b was done at a small scale
with chromatographic workup.
compound 13d as the dominant product accompanied by
unreacted 12d and polar byproducts. The reaction mixture
was extracted with CH2Cl2, washed with water to remove
salt and imidazole, and the resulting residue was purified
by vacuum filtration through a pad of silica followed by
trituration with methanol, affording 13d in 48% yield
(entry 7). Treatment of 13d with TBAF in THF gave 4
accompanied by a small amount of polar byproducts.
Vacuum filtration of the crude mixture through a pad of
silica followed by trituration with methanol afforded 4 in
88% yield (Scheme 4). In summary, the synthesis of
pure perylene-monoimide dyes 13a–d was achieved by
imidation of perylene-anhydride 9. For preparative scale
syntheses, the use of vacuum filtration, precipitation, and
trituration proved to be a viable substitute for chroma-
tography and extraction procedures.
The reaction conditions found to be best [Zn(OAc)2·2H2O
in imidazole/mesitylene at 1308C] in preparing 13b were
applied to prepare other perylene-monoimides bearing
different N-aryl units. In this manner, perylene-monoimide
13c was prepared in 30% yield (entry 5), also at a small
scale with chromatographic workup. The synthesis of
perylene-monoimide 4, which has a free ethyne on the
aniline component, could not be obtained via imidation
with anhydride 9, probably due to decomposition during
the long reaction (entry 6). However, the TIPS-protected
ethynylaniline 12d reacted with anhydride 9 affording
We also found that perylene-monoimide 13a could be used
as a starting material for preparing perylene-anhydride 9
(Scheme 5). The conditions employed were similar to those
in the synthesis of 9 from 11 (Scheme 2). Perylene 13a was
refluxed with KOH in 2-methyl-2-propanol for 2 h. After
treatment with acetic acid followed by addition of water,
anhydride 9 was obtained as a pre-cipitate which was
purified by vacuum filtration through a pad of silica and
trituration with methanol. These results show that the
perylene-monoimide bearing an unhindered N-imide aryl
group can be converted to the perylene-anhydride in
excellent yield.
2.2. Synthesis of perylene–porphyrin building blocks
lacking isopropyl groups
We previously prepared bis(perylene)porphyrin building
blocks wherein each perylene-monoimide dye was substi-
tuted with two isopropyl substituents on the N-imide aryl
group, as well as with three aryloxy groups at the perimeter
of the perylene (14, 15, Chart 4).21 Building block 14 is an
ABCD-porphyrin that bears one iodo group and one ethyne
group in a trans architecture for Sonogashira coupling,
while 15 is a trans-AB2C-porphyrin that bears two ethyne
groups for Glaser coupling. The Y-shaped architecture of
14 and 15 was designed to preclude cofacial aggregation of
the porphyrin macrocycles while still maintaining efficient
energy transfer from the perylene to the porphyrin. Indeed,
14 and 15 exhibit efficient energy transfer from perylene to
porphyrin, are highly soluble in organic solvents, and were
converted into rod-like oligomers that also exhibited high
solubility.21
Scheme 4.

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K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
coupling of bromo-perylene (8) and 3,5-diethynylbenzalde-
hyde (19,30 8.9% yield, entry 2). The disparity in coupling
yield is easily attributed to the less active bromine at the
4-position of the perylene N-imide substituted aryl moiety
compared with the bromines at the 3 and 5-positions of
benzaldehyde.20 The availability of iodo-perylene 13c
presented an opportunity to perform the coupling with a
more active halogen on the perylene-monoimide dye. Thus,
Sonogashira coupling of 13c with 19 afforded 20 in 42%
yield (entry 3). This result was somewhat improved
compared with the combination of bromo-perylene and 19
(8.9% yield); however, the use of the ethynyl-perylene and
18 provided the best yields in the preparation of bis(peryl-
ene)benzaldehyde 20.
Sonogashira coupling of ethynyl-perylene 57 and 18
afforded perylene-aldehyde 21 in 35% yield (entry 4 in
Table 2, Scheme 6). The coupling reaction was performed in
toluene/triethylamine (10:1) at 608C with the perylene at
a concentration of 14 mM. Unfortunately, compound 21
exhibited poor solubility (,1 mg/mL in CDCl3) and
attempts to prepare the corresponding tetrakis(perylene)-
porphyrin by condensation of 21 with 5-mesityldipyrro-
methane29 proved unsuccessful. No further studies were
performed with 21. A bis(perylene)benzaldehyde lacking
isopropyl groups (22) was prepared by Sonogashira
coupling of 13a (2.4 equiv.) and 18 in the presence of CuI
in 69% yield (entry 5).20 The reaction mixture was initially
heterogeneous, became homogeneous upon increasing
the temperature, and afforded aldehyde 22 as a precipitate,
indicating limited solubility. In summary, the solubility of
the bis(perylene)benzaldehydes increases in the following
series: 21 (isopropyl groups but only one aryloxy
substituent),22 (no isopropyl groups but three aryloxy
substituents),20 (isopropyl groups and three aryloxy
substituents).
Scheme 5.
Early in the development of perylene-imide dyes, it became
apparent that bulky N-imide groups were essential for
achieving workable solubility in organic solvents.22,23,27
Aryloxy substituents were subsequently introduced at
the perimeter of the perylene thereby further increasing
the solubility.10,11 Given the Y-shaped architecture of the
bis(perylene)porphyrins, we wondered whether the alkyl
groups on the N-imide aryl group, or fewer 4-tert-
butylphenoxy groups, were in fact essential for solubility
of the bis(perylene)porphyrins. The availability of the
new perylene-monoimide dyes provided an opportunity to
address this question, prompting us to prepare the perylene–
porphyrins 16 and 17 (Chart 4), which are analogs of 14 and
15.
The synthesis of dipyrromethanes is readily achieved at
room temperature by the reaction of an aldehyde in excess
neat pyrrole (25:1 molar ratio of pyrrole–aldehyde) upon
addition of a catalytic amount of TFA.29 Very recently, we
found that the dipyrromethane synthesis with 20 performed
with inclusion of a small amount of CH2Cl2 (3:1 v:v pyrrole/
CH2Cl2) and a much larger molar ratio of pyrrole–aldehyde
(400:1) affords a significant enhancement in the yield.21
The CH2Cl2 in this case was essential to solubilize the
bis(perylene)benzaldehyde 20, which was insoluble in neat
pyrrole, but apparently the slight dilution achieved in doing
so as well as the increased pyrrole–aldehyde ratio is quite
beneficial to the synthesis. We employed the same modified
method here. Thus, the reaction of aldehyde 22 and excess
pyrrole (400-fold) in CH2Cl2 (25% by volume) using TFA
as a catalyst gave bis(perylene)dipyrromethane 23 in 96%
yield (Scheme 7). Dipyrromethane 23 served as a key
compound for preparing the perylene–porphyrin monomers
required in Sonogashira and Glaser polymerizations.
The synthesis of porphyrins bearing distinct patterns of
meso-substituents can be achieved in a rational manner by
reaction of a dipyrromethane and a dipyrromethane–
dicarbinol.28 The synthesis of a dipyrromethane requires
access to the corresponding precursor aldehyde.29 A 3,5-bis-
(perylene)benzaldehyde and the corresponding bis(peryl-
ene)phenyldipyrromethane served as valuable intermediates
in the synthesis of perylene–porphyrin building blocks 14
and 15.21 This same approach was employed in the synthesis
of 16 and 17.
The dipyrromethaneþdipyrromethane–dicarbinol conden-
sation leading to meso-substituted porphyrins has typically
been carried out at room temperature in CH3CN using TFA
catalysis.28 The choice of catalytic conditions is essential to
avoid acidolysis of the dipyrromethane followed by
undesired recombination of fragments, leading to a mixture
We found previously that the Sonogashira coupling to make
the bis(perylene)benzaldehyde 20 was very sensitive to the
type of substituent on the N-aryl moiety. For example, the
synthesis of 20 via coupling of ethynyl-perylene 4 with
commercially available 3,5-dibromobenzaldehyde (18, 83%
yield, entry 1 in Table 2, Scheme 6) was superior to the

K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1197
Chart 4.
of porphyrins (i.e. scrambling). Recently we found that
the use of selected mild, Lewis acids in CH2Cl2 at room
temperature affords the porphyrin without detectable
scrambling and often with higher yields than that obtained
with TFA in CH3CN.31 We employed the new acid catalysis
conditions in this work. Thus, the condensation of 23 with
24-diol, which is obtained from reduction of the diacyl-
dipyrromethane 24 using NaBH4 in THF/methanol (10:1),
was performed in the presence of Yb(OTf)3 in CH2Cl2 at
room temperature. Subsequent oxidation with DDQ and
metalation with Zn(OAc)2·2H2O at room temperature
afforded porphyrin 16 in 10% yield. In the same manner,
Table 2. Sonogashira couplling of ethynyl/halide–perylene and dibromo/diethynyl-benzaldehyde
Entry
R1
R2
R3
R4
Perylene
Aldehyde
Compound (peryleneþaldehyde)
Yield (%)
1
2
3
4
5
4-t-Butylphenoxy
4-t-Butylphenoxy
4-t-Butylphenoxy
H
i-Pr
i-Pr
i-Pr
i-Pr
H
CuCH
Br
I
CuCH
CuCH
Br
4
8
13c
5
13a
18
19
19
18
18
20
20
20
21
22
83
8.9a
42b
35c
69
CuCH
CuCH
Br
4-t-Butylphenoxy
Br
The Pd-coupling reaction was carried out under the following conditions unless otherwise noted: [perylene]¼12 mM, [aldehyde]¼5.0 mM, catalysts¼
Pd2(dba)3, PPh3, and Cul, solvent¼toluene/TEA (5:1), temperature¼508C (Ref. 20).
a
[Perylene]¼10 mM, [aldehyde]¼5.0 mM, Pd2(dba)3 and P(o-tol)3, 608C (Ref. 20).
b
Pd2(dba)3, P(o-tol)3, 408C.
[Perylene]¼14 mM, [aldehyde]¼6.0 mM, Pd2(dba)3, P(o-tol)3, toluene/TEA (10:1), 608C.
c

1198
K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
Scheme 6.
porphyrin 17 was prepared by the condensation of
dipyrromethane 23 and 25-diol in 31% yield. In both
cases, no scrambling was detected upon mass spectral
analysis of the crude reaction samples. However, both
perylene–porphyrins 16 and 17 have lower solubility than
their analogs bearing isopropyl groups (14, 15).
The Glaser reaction of 17 was carried out with Pd(PPh3)2Cl2
and CuI in toluene/diisopropylethylamine at room tempera-
ture in the presence of air. A slight amount of precipitation
appeared to form. After 3 h, analytical SEC of a dissolved
reaction sample showed a distribution of the starting
monomer and oligomers up to the octamer stage. The
monomer, dimer, reagents and small byproducts were
removed by preparative SEC. The resulting crude product
was further purified by triturating with methanol and
hexanes. The resulting magenta powder could be dissolved
in THF, was partially soluble in CHCl3 and CH2Cl2, but was
only slightly soluble in toluene. While the diphenylbuta-
diyne-linked oligomers (Glaser reaction) appeared to be
more soluble than the diphenylethyne-linked oligomers
(Sonogashira reaction), further characterization of the
oligomers derived from bis(perylene)porphyrins 16 and 17
was not attempted.
2.3. Oligomeric bis(perylene)porphyrin arrays
We previously subjected perylene–porphyrin building
blocks to Sonogashira and Glaser polymerizations, afford-
ing diphenylethyne- or diphenylbutadiyne-linked oligo-
mers, respectively.21 The oligomers were of considerable
size and exhibited adequate solubility in common organic
solvents (THF, CHCl3, CH2Cl2, toluene) for routine
processing and characterization. The same routes were
employed for preparing oligomers of bis(perylene)por-
phyrin monomers lacking isopropyl groups.
To investigate the optical properties of a tetrakis(peryl-
ene)porphyrin wherein each perylene lacks isopropyl
substituents, we prepared porphyrin 27 (Scheme 8).
Bis(perylene)benzaldehyde 22 and 5-mesityldipyrro-
methane (26)29 were condensed at room temperature in
CH2Cl2 with TFA catalysis, conditions that are known to
afford reaction without scrambling.32 Oxidation with DDQ
and metalation with Zn(OAc)2·2H2O at room temperature
afforded porphyrin 27 in 8.8% yield. Compound 27 is
soluble in CHCl3 but could hardly be dissolved in CH2Cl2 or
toluene. Indeed, a sample was marginally soluble in toluene
at the mM concentration, requiring warming and sonication
to collect a visible absorption spectrum. In contrast, the
analogous tetrakis(perylene)porphyrin wherein each peryl-
ene bears two isopropyl groups on the N-imide aryl group,20
was highly soluble in CHCl3, CH2Cl2 or toluene.
A Sonogashira polymerization of 16 was performed under
argon at room temperature in the presence of Pd2(dba)3 and
AsPh3 in toluene/triethylamine. After 22 h, the reaction
mixture became heterogeneous and analytical size exclu-
sion chromatography (SEC) of a dissolved sample revealed
the formation of oligomers up to the pentamer stage. The
amount of these oligomers increased slightly after 40 h.
Analytical SEC of the suspended solid in the reaction
mixture (obtained by dissolving the solid in THF with
sonication) showed the presence of short oligomers. The
low solubility of these short oligomers likely impeded
the formation of longer oligomers. Therefore, we next
examined the Glaser polymerization, which typically is
more rapid and gives longer oligomers compared with those
given by Sonogashira coupling.21

K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1199
Scheme 7.
The absorption spectrum of 27 displayed the characteristic
bands of the zinc porphyrin and the perylene-monoimide.
The Soret band of the zinc porphyrin was sharp (fwhm¼13
interactions between the porphyrin and perylenes are
rather weak. However, excitation at 540 nm, where the
perylene-monoimide absorbs preferentially, resulted in
emission predominantly from the zinc porphyrin. The
spectral data, which are nearly identical to those of the
nm) and resembled that of
a porphyrin lacking
perylene substituents, indicating that any electronic

1200
K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
Scheme 8.
tetrakis(perylene)porphyrin analog bearing isopropyl
groups flanking the N-imide position,20 are indicative
of efficient energy transfer from the perylene-monomide
units to the porphyrin. Thus, the perylene-monoimide
dyes in 27 provide absorption in the spectral region
where the porphyrin absorbs weakly, do not alter the energy
levels of the porphyrin as shown by the absorption
spectrum, and transfer energy to the porphyrin with good
efficiency, all of which are features of viable accessory
pigments.
3. Conclusions
The synthesis of perylene-anhydride 9 enables the prepa-
ration of a family of perylene-monoimide dyes that differ
only in the type of synthetic handle and solubilizing groups
on the N-imide unit. This synthetic strategy has been
implemented to minimize use of chromatography, relying
instead on selective precipitation, trituration, filtration, and
filtration over short pads of silica. Perylene-monoimide dyes
were prepared that either incorporate or lack two isopropyl

K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1201
groups at the 2,6-positions flanking the N-imide substituent
on the aryl unit. The best method for preparing the dyes
employs imidation of perylene-anhydride 9 with an aniline
derivative in imidazole/mesitylene containing Zn(OAc)2·2-
H2O at 1308C. Two bis(perylene)porphyrin building blocks
were prepared for Sonogashira and Glaser oligomerizations;
one tetrakis(perylene)porphyrin array was prepared for
fundamental spectroscopic studies. In each case, the
perylene-monoimide dyes lacked isopropyl groups flanking
the N-imide substituent. Each of the perylene–porphyrin
monomers was sufficiently soluble for spectroscopic
characterization and routine handling, though each array
was less soluble than the analog in which the isopropyl
groups were present. The solubility differences were
exacerbated upon formation of diphenylethyne or diphe-
nylbutadiyne-linked oligomers. The monomers lacking
the isopropyl groups afforded oligomers that were shorter,
owing to precipitation during the course of polymerization,
than the oligomers derived from monomers in which
the isopropyl groups were present. On the other hand, the
synthesis of a bis(perylene)benzaldehyde (21) bearing the
two flanking isopropyl groups but incorporating only one
aryloxy substituent gave very poor solubility compared with
that containing three aryloxy groups (20). Thus, adequate
solubility of perylene–porphyrin arrays and oligomers
requires the presence of two types of solubilizing features:
three aryloxy groups at the perylene perimeter and two
isopropyl groups flanking the N-imide moiety.
purchased from Aldrich and Fisher and used as received.
Chloroform contained 0.8% ethanol as a stabilizer.
4.2. Non-commercial compounds
Compounds 12c26 and 19;30 diacyldipyrromethanes 2421
and 25;35 and 5-mesityldipyrromethane (26)29 were pre-
pared as described in the literature.
4.3. New synthetic compounds and procedures
4.3.1. N-(2,5-Di-tert-butylphenyl)perylene-3,4-dicarboxi-
mide (2). Following the procedure of Langhals,9 samples of
3 (33.0 g, 84.2 mmol), 2,5-di-tert-butylaniline (9.47 g,
46.0 mmol), Zn(OAc)2·2H2O (3.97 g, 18.1 mmol), imida-
zole (169 g), and H2O (72 mL) were placed in an autoclave
equipped with a manometer. The mixture was stirred at
1908C. After 20 h, the manometer showed 15 bar and the
reaction mixture was cooled to room temperature. Water
(300 mL) was added to the reaction mixture. The resulting
mixture was vacuum filtered over a single fritted glass filter.
The filtered solid obtained was washed with 2N aqueous
HCl/methanol [500 mL, (1:1)] then H2O/methanol [300 mL,
(1:1)] and dried in an oven at 1308C. TLC analysis (silica,
CH2Cl2) showed the presence of the title compound
(Rf¼0.52, red) and 1 (Rf¼0.21, orange). The crude solid
was suspended in CH2Cl2 (300 mL) and vacuum filtered
through a fritted glass filter, then washed with CH2Cl2
(500 mL) leaving insoluble byproducts on the filter. The
filtrate was concentrated to a volume of ,300 mL and
passed through a pad of silica (6.0£6.0 cm, swelled with
CH2Cl2) in a fritted glass filter with CH2Cl2 (500 mL). A
less polar, slightly yellow byproduct (perylene itself) eluted
first and was not collected. Subsequent elution with CH2Cl2
(800 mL) afforded the title compound. The filtrate was
concentrated to a volume of ,200 mL. Then methanol
(200 mL) was added. A red solid precipitated upon standing
at 08C and was collected by filtration (12.7 g). The purity of
the title compound obtained was estimated to be 90% [1
accounts for the remaining 10%] by 1H NMR spectroscopy.
The yield is estimated to be 49% assuming the purity to be
90%. This material was used without further purification in
the next step.
4. Experimental
4.1. General
1H NMR spectra (300 or 400 MHz) and 13C (75 MHz) were
recorded in CDCl3. Mass spectra of porphyrins and
perylene–porphyrin compounds were obtained by high-
resolution fast atom bombardment (FAB-MS) and by
matrix-assisted laser desorption ionization mass spec-
trometry (MALDI-MS). Absorption and emission spectra
were collected in toluene at room temperature. Melting
points are uncorrected. An autoclave (Roth Hochdruck-
Laborautoklav Modell IV, Carl Roth GmbH & Co. KG,
Karlsruhe, Germany) equipped with a voltage transformer
(Simran, SM-1000DE) was used. Centrifugation was
4.3.2. 1,6,9-Tribromo-N-(2,5-di-tert-butylphenyl)pery-
lene-3,4-dicarboximide (10). Following the approach out-
lined by Mu¨llen10 and the procedure described in detail by
Wasielewski,14 a mixture containing crude 2 (13.3 g,
assuming 26.1 mmol) and Br2 (21.0 mL, 410 mmol) in
CHCl3 (400 mL) was refluxed for 19 h. The reaction
mixture was concentrated to dryness. TLC analysis (silica,
CH2Cl2) showed the presence of the title compound
(Rf¼0.83, red), a major byproduct (Rf¼0.73, orange), and
residual 1 (Rf¼0.20, orange). The crude solid was
suspended in toluene/hexanes [400 mL (1:1)] and vacuum
filtered through a pad of silica [6.0£6.0 cm, swelled with
toluene/hexanes (1:1)] in a fritted glass filter. Elution with
toluene/hexanes [1.0 L (1:1)] removed a small amount of a
yellow material; then elution with toluene/hexanes [3.0 L
(1:1)] afforded the title compound in ,90% purity. Most of
the impurities (the major byproduct and 1) remained at the
top of the silica pad. The eluant containing the title
compound (,90% purity with an unknown compound
performed using
a Dynac II tabletop centrifuge
(4000 rpm). Sonication was performed using a Fisher
FS14 tabletop sonication bath. Silica gel (Baker 40 mm
average particle size) was used for vacuum filtration and
column chromatography. Preparative SEC was performed
using Biorad Bio-Beads SX-1 (200–400 mesh). Analytical
SEC was performed using an HP 1100 Series Liquid
4
3
˚
˚
Chromatograph (column size¼a 10 A column and a 10 A
column in series; flow rate¼0.800 mL/min; solvent¼THF;
quantitation at 420 and 510 nm; reference at 670 nm; oven
temperature 258C).33 All Sonogashira coupling reactions
were performed using a Schlenk line. All Glaser coupling
reactions were performed in air using Pd(PPh3)2Cl2 and CuI.
Palladium insertion and transmetalation of porphyrins have
not been observed under these conditions.34 Toluene and
triethylamine were freshly distilled from CaH2 and sparged
of oxygen prior to use. All solvents and reagents were

1202
K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
constituting the remaining ,10%) was concentrated to
dryness. Addition of CH2Cl2 (100 mL) yielded a slurry, to
which hexanes (200 mL) was added. The resulting red solid
was collected by filtration (6.22 g, 32%). Characterization
data were identical to those reported previously.14
CH2Cl2/hexanes [2.0 L (2:1)] eluted the title compound.
The filtrate was concentrated to dryness. The solid was
triturated with a small volume of methanol then filtered,
affording a deep-purple solid (3.52 g, 63%): mp 152–
1
1548C; H NMR d 1.33 (s, 9H), 1.35 (s, 9H), 1.36 (s, 9H),
6.87 (d, J¼8.8 Hz, 1H), 6.99 (d, J¼8.8 Hz, 2H), 7.05 (d,
J¼8.8 Hz, 2H), 7.10 (d, J¼8.8 Hz, 2H), 7.39 (d, J¼8.8 Hz,
2H), 7.42–7.45 (m, 4H), 7.61–7.67 (m, 1H), 8.14 (s, 1H),
8.17 (s, 1H), 8.52 (d, J¼8.1 Hz, 1H), 9.23 (d, J¼8.8 Hz,
1H), 9.43 (d, J¼7.3 Hz, 1H); 13C NMR d 31.6, 34.6, 111.3,
115.5, 116.6, 118.6, 118.8, 120.3, 121.5, 124.8, 125.1,
125.4, 125.7, 126.7, 127.1, 127.3, 127.4, 127.5, 128.3,
128.6, 130.3, 130.7, 131.2, 147.6, 147.8, 148.0, 152.7,
153.2, 153.3, 153.6, 156.8, 160.1; MALDI-MS (dithranol)
obsd 765.0 [Mþ]; FAB-MS obsd 766.3315, calcd 766.3294;
labs 410, 533 nm; lem (lex¼500 nm) 578 nm. Anal. calcd
for C52H46O6: C, 81.44; H, 6.05; Found: C, 81.17; H, 6.19.
4.3.3. 1,6,9-Tris(4-tert-butylphenoxy)-N-(2,5-di-tert-
butylphenyl)perylene-3,4-dicarboximide (11). Following
a procedure described for diaryloxylation14 but at higher
temperature and with excess 4-tert-butylphenol to achieve
triaryloxylation, a mixture of 10 (9.90 g, 13.3 mmol), 4-tert-
butylphenol (24.0 g, 160 mmol), and K2CO3 (26.5 g,
192 mmol) in anhydrous DMF (500 mL) was refluxed for
1 h. The reaction mixture was cooled to room temperature.
TLC analysis [silica, CH2Cl2/hexanes (1:2)] showed the
presence of the title compound (Rf¼0.37, magenta) and a
major byproduct (Rf¼0.23, purple). Water (500 mL) was
added to the reaction mixture. The resulting solid was
collected by vacuum filtration in a fritted glass filter, washed
with H2O/methanol [500 mL (1:1)] while on the filter, and
then dried in an oven at 1308C. The crude solid consisted of
the title compound and a major byproduct. The crude solid
was dissolved in CH2Cl2/hexanes [400 mL (1:4)] and
vacuum filtered through a pad of silica [9.5£6.0 cm, swelled
with CH2Cl2/hexanes (1:4)] on a fritted glass filter using
CH2Cl2/hexanes [6.0 L (1:4)]. The byproduct remained on
the silica pad. The filtrate was concentrated to give a
4.3.5. 2,6-Diisopropyl-4-[2-(triisopropylsilyl)ethynyl]-
aniline (12d). Following a general procedure,36 a mixture
of 12c (5.00 g, 16.5 mmol), Pd(PPh3)2Cl2 (116 mg,
0.165 mmol) and CuI (31.4 mg, 0.165 mmol) was placed
in a Schlenk flask then degassed triethylamine (50 mL) was
added to the mixture. (Triisopropylsilyl)acetylene
(4.50 mL, 20.1 mmol) was added and the mixture was
stirred at room temperature for 16 h. The mixture was
concentrated and taken up in ether. The resulting mixture
was filtered and concentrated to dryness. Vacuum filtration
through a pad of silica [9.5£6.0 cm, CH2Cl2/hexanes
(4:1!2:1)] on a fritted glass filter afforded a faint yellow
1
magenta solid (6.90 g, 54%): mp 203–2058C; H NMR d
1.25 (s, 9H), 1.28 (s, 9H), 1.31 (s, 9H), 1.335 (s, 9H), 1.344
(s, 9H), 6.89–6.93 (m, 2H), 7.02 (d, J¼8.8 Hz, 2H), 7.08 (d,
J¼8.8 Hz, 2H), 7.09 (d, J¼8.8 Hz, 2H), 7.37 (d, J¼8.8 Hz,
2H), 7.40–7.44 (m, 5H), 7.52–7.55 (m, 1H), 7.62–7.67 (m,
1H), 8.28 (s, 1H), 8.31 (s, 1H), 8.48 (d, J¼8.1 Hz, 1H), 9.26
(d, J¼8.8 Hz, 1H), 9.46 (d, J¼8.1 Hz, 1H); 13C NMR d
31.4, 31.7, 32.0, 34.4, 34.6, 35.7, 111.9, 118.6, 118.8, 119.9,
120.9, 121.9, 122.5, 123.3, 124.4, 124.7, 126.1, 126.3,
126.5, 126.6, 126.8, 127.1, 127.3, 127.5, 127.7, 127.8,
128.0, 128.9, 129.9, 130.0, 130.9, 131.7, 132.9, 143.9,
147.2, 147.3, 147.7, 150.1, 152.9, 153.6, 153.7, 156.1,
164.5; MALDI-MS (dithranol) obsd 896.4 [(M2t-butyl)þ],
952.3 [Mþ]; FAB-MS obsd 953.4997, calcd 953.5019; labs
415, 531 nm; lem (lex¼500 nm) 571 nm. Anal. calcd for
C66H67NO5: C, 83.07; H, 7.08; N, 1.47; Found: C, 82.99; H,
7.42; N, 1.58.
1
oil (5.20 g, 88%): H NMR d 1.17 (m, 18H), 1.29 (d, J¼
6.8 Hz, 12H), 2.86–2.92 (m, 2H), 3.93 (brs, 2H), 7.19 (s,
2H); 13C NMR d 11.4, 18.7, 22.2, 27.8, 86.6, 109.0, 112.7,
127.0, 132.0, 140.8; FAB-MS obsd 357.2845, calcd
357.2852. Anal. calcd for C23H39NSi: C, 77.24; H, 10.99;
N, 3.92; Found: C, 77.17; H, 11.11; N, 3.96.
4.3.6. 2,6-Diisopropyl-4-[2-(trimethylsilyl)ethynyl]aniline
(12e). Following a general procedure,36 samples of 12c
(2.50 g, 8.25 mmol), Pd(PPh3)2Cl2 (58.0 mg, 82.5 mmol)
and CuI (15.7 mg, 82.5 mmol) were placed in a Schlenk
flask, then degassed triethylamine (30 mL) was added to the
mixture. (Trimethylsilyl)acetylene (1.28 mL, 9.08 mmol)
was added and the mixture was stirred at room temperature
for 16 h. The mixture was concentrated and taken up in
ether. The resulting mixture was filtered and concentrated
to dryness. Vacuum filtration through a pad of silica
[6.0£6.0 cm, CH2Cl2/hexanes (3:1)] on a fritted glass filter
afforded an orange oil that slowly crystallized (1.94 g,
86%): mp 69–728C; 1H NMR d 0.24 (s, 9H), 1.24 (d,
J¼6.9 Hz, 12H), 2.83–2.88 (m, 2H), 3.89 (brs, 2H), 7.16 (s,
2H); 13C NMR d 0.2, 22.2, 27.7, 90.4, 107.2, 112.0, 126.9,
131.9, 141.1; FAB-MS obsd 273.1905, calcd 273.1913.
Anal. calcd for C17H27NSi: C, 74.66; H, 9.95; N, 5.12;
Found: C, 74.41; H, 9.90; N, 5.09.
4.3.4. 1,6,9-Tris(4-tert-butylphenoxy)-3,4-dicarboxylic
anhydride (9). Following a standard procedure,9,14
a
mixture of 11 (6.90 g, 7.23 mmol) and KOH (21.0 g,
374 mmol) in 2-methyl-2-propanol (400 mL) was refluxed
for 2 h, affording quantitative hydrolysis of the imide. The
hot reaction mixture was poured into acetic acid (800 mL)
and the mixture was vigorously stirred for 5 min at room
temperature. To this mixture was added H2O (1.0 L). The
resulting precipitate was collected by vacuum filtration. The
precipitate was washed with H2O and dried in an oven at
1308C. TLC analysis [silica, CH2Cl2/hexanes (1:1)] showed
the presence of a small amount of a magenta product
(Rf¼0.92, consistent with reformation of 11) and the title
compound (Rf¼0.57, magenta). The crude solid was
dissolved in CH2Cl2/hexanes [300 mL (1:3)] and vacuum
filtered through a pad of silica (9.5£6.0 cm, swelled with
hexanes) on a fritted glass filter. Elution with CH2Cl2/-
hexanes [3.0 L (2:3)] removed a less polar byproduct, then
4.3.7. 2,6-Diisopropyl-4-ethynylaniline (12f). A mixture
of 12e (1.40 g, 5.12 mmol) and TBAF on silica gel (7.68 g,
,1.1 mmol/g) in THF (120 mL) containing 0.1% water was
stirred at room temperature for 1 h. TLC analysis (silica,
CHCl3) showed the complete removal of the trimethylsilyl
group. The reaction mixture was washed with 10% aqueous
NaHCO3 and water, then dried over Na2SO4. Vacuum

K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1203
filtration through a pad of silica [6.0£6.0 cm, CH2Cl2/
hexanes (1:2)] on a fritted glass filter afforded an orange oil
(629 mg, 61%): 1H NMR d 1.26 (d, J¼6.4 Hz, 12H), 2.82–
2.92 (m, 2H), 2.97 (s, 1H), 3.91 (brs, 2H), 7.19 (s, 2H); 13C
NMR d 22.2, 27.8, 74.2, 85.5, 110.9, 127.1, 132.1, 141.3;
FAB-MS obsd 201.1516, calcd 201.1517. Anal. calcd for
C14H19N: C, 83.53; H, 9.51; N, 6.96; Found: C, 83.54; H,
9.54; N, 7.04.
extracts were combined, dried (Na2SO4), and concentrated.
The crude mixture obtained was purified by three silica
column chromatography procedures [(1) toluene, (2)
CH2Cl2/hexanes (2:3), and (3) toluene]. The desired fraction
was concentrated to dryness. The resulting solid was treated
with methanol and the mixture was centrifuged. The
supernatant was decanted, leaving
a magenta solid
1
(24 mg, 40%): mp 174–1768C; H NMR d 1.14 (d, J¼
6.6 Hz, 12H), 1.32 (s, 9H), 1.34 (s, 9H), 1.35 (s, 9H), 2.66–
2.76 (m, 2H), 6.90 (d, J¼8.8 Hz, 1H), 7.02 (d, J¼8.1 Hz,
2H), 7.08 (d, J¼8.1 Hz, 2H), 7.10 (d, J¼8.1 Hz, 2H), 7.29
(d, J¼8.1 Hz, 2H), 7.37 (d, J¼8.8 Hz, 2H), 7.39–7.46 (m,
5H), 7.62–7.67 (m, 1H), 8.30 (s, 1H), 8.34 (s, 1H), 8.48 (d,
J¼8.1 Hz, 1H), 9.25 (d, J¼8.8 Hz, 1H), 9.45 (d, J¼8.1 Hz,
1H); 13C NMR d 24.0, 29.0, 29.7, 31.5, 34.36, 34.39, 34.44,
111.6, 118.1, 118.2, 119.8, 120.5, 121.4, 122.1, 123.5,
123.9, 124.2, 124.7, 124.9, 125.8, 126.6, 126.9, 127.0,
127.1, 127.6, 127.7, 127.9, 129.3, 129.7, 129.8, 130.7,
130.8, 131.5, 145.6, 146.8, 147.0, 147.5, 152.4, 153.3,
153.4, 155.9, 163.2; MALDI-MS (dithranol) obsd
925.0 [Mþ]; FAB-MS obsd 925.4718, calcd 925.4706
(C64H63NO5); labs (log 1) 412 (3.8), 533 (4.5) nm; lem
(lex¼530 nm) 573, 622 (sh) nm.
4.3.8. Preparative-scale imidation procedure using
DMF/Zn(OAc)2·2H2O, exemplified for 1,6,9-tris(4-tert-
butylphenoxy)-N-(4-ethynylphenyl)perylene-3,4-dicarb-
oximide (13a). Following a procedure modified from that of
Langhals,9 a mixture of 9 (3.25 g, 4.24 mmol), 12a (1.49 g,
12.7 mmol, 3 equiv.), and Zn(OAc)2·2H2O (850 mg,
3.87 mmol) in anhydrous DMF (100 mL) was stirred at
1308C for 17 h. TLC analysis [silica, CH2Cl2/hexanes (1:1)]
showed the presence of the title compound (Rf¼0.63,
magenta), a small amount of 9 (Rf¼0.58, magenta), a small
amount of a byproduct (Rf¼0.50, magenta), and the excess
12a near the origin. The reaction mixture was cooled to
room temperature and water (200 mL) was added. The
resulting solid was collected by vacuum filtration on a
fritted glass filter and washed with H2O/methanol [300 mL
(1:1)] to remove 12a. The damp solid was dissolved in
CH2Cl2 (300 mL). The solution was dried (Na2SO4),
filtered, and the filtrate was concentrated to dryness. The
crude solid was dissolved in toluene/hexanes [400 mL (1:1)]
and vacuum filtered through a pad of silica [6.0£6.0 cm,
swelled with toluene/hexanes (1:1)] on a fritted glass filter.
Elution with toluene/hexanes [1.0 L (1:1)] removed a less
polar byproduct, then toluene/hexanes [2.5 L (3:2)] eluted
the title compound. The filtrate was concentrated to dryness.
The solid was triturated with methanol then filtered,
4.3.10. 1,6,9-Tris(4-tert-butylphenoxy)-N-(2,6-diisopropyl-
4-iodophenyl)perylene-3,4-dicarboximide (13c). Following
the small-scale procedure used to prepare 13b, a mixture
of 9 (365 mg, 0.475 mmol), 12c (434 mg, 1.43 mmol,
3 equiv.) and Zn(OAc)2·2H2O (95.0 mg, 0.431 mmol) in
imidazole (1.9 g) and mesitylene (3.0 mL) was stirred at
1308C. After 23 h, the reaction mixture was cooled to room
temperature and 2N aqueous HCl was added. The aqueous
phase was extracted with CH2Cl2. The CH2Cl2 extracts were
combined, dried (Na2SO4), and concentrated. The crude
mixture obtained was purified by column chromatography
(silica, toluene). The desired fraction was concentrated
to dryness. The solid was treated with methanol and the
mixture was centrifuged. The supernatant was decanted,
1
affording a magenta solid (1.84 g, 50%): mp .2308C; H
NMR d 1.31 (s, 9H), 1.33 (s, 9H), 1.34 (s, 9H), 3.12 (s, 1H),
6.91 (d, J¼8.8 Hz, 1H), 7.01 (d, J¼8.8 Hz, 2H), 7.07 (d, J¼
8.1 Hz, 2H), 7.09 (d, J¼8.8 Hz, 2H), 7.23–7.26 (overlapped
with solvent peak, 2H), 7.36 (d, J¼8.8 Hz, 2H), 7.41 (d,
J¼8.8 Hz, 2H), 7.42 (d, J¼8.1 Hz, 2H), 7.60–7.68 (m, 3H),
8.24 (s, 1H), 8.27 (s, 1H), 8.49 (d, J¼8.1 Hz, 1H), 9.28 (d,
J¼8.8 Hz, 1H), 9.48 (d, J¼8.1 Hz, 1H); 13C NMR d 31.42,
31.44, 31.5, 78.0, 83.0, 111.7, 118.4, 118.6, 118.7, 119.8,
120.0, 121.0, 122.1, 122.5, 122.9, 124.1, 124.4, 125.8,
126.6, 126.9, 127.1, 127.2, 127.3, 127.4, 127.66, 127.68,
128.7, 129.9, 130.0, 130.6, 131.4, 133.0, 135.6, 147.1,
147.3, 147.5, 152.7, 153.36, 153.40, 153.5, 153.6, 156.1,
163.20, 163.22; MALDI-MS (dithranol) obsd 865.4
[Mþ], 1013.5 [(Mþ148)þ]; FAB-MS obsd 865.3783,
calcd 865.3767 (C60H51NO5); labs (log 1) 413 (3.8), 531
(4.6) nm; lem (lex¼500 nm) 574 nm.
1
leaving a magenta solid (150 mg, 30%): mp .2308C; H
NMR d 1.11 (d, J¼6.6 Hz, 12H), 1.32 (s, 9H), 1.34 (s, 9H),
1.35 (s, 9H), 2.59–2.68 (m, 2H), 6.90 (d, J¼8.8 Hz, 1H),
7.01 (d, J¼8.1 Hz, 2H), 7.05–7.11 (m, 4H), 7.36 (d, J¼
8.1 Hz, 2H), 7.41 (d, J¼8.8 Hz, 2H), 7.43 (d, J¼8.1 Hz,
2H), 7.58 (s, 2H), 7.62–7.68 (m, 1H), 8.29 (s, 1H), 8.32 (s,
1H), 8.49 (d, J¼8.8 Hz, 1H), 9.25 (d, J¼8.8 Hz, 1H), 9.45
(d, J¼8.1 Hz, 1H); 13C NMR d 24.0, 29.2, 31.7, 34.6,
96.3, 111.8, 118.3, 118.4, 120.0, 120.3, 121.3, 122.2, 123.8,
124.6, 125.0, 126.0, 126.8, 127.1, 127.3, 127.8, 128.0,
128.3, 130.0, 130.2, 130.9, 131.2, 131.8, 133.7, 147.1,
147.3, 147.8, 148.4, 152.6, 153.5, 153.6, 156.3, 163.3;
MALDI-MS (dithranol) obsd 1050.6 [Mþ], 925.9
[(M2I)þ]; FAB-MS obsd 1051.3680, calcd 1051.3673
(C64H62INO5); labs (log 1) 413 (3.6), 537 (4.5) nm; lem
(lex¼500 nm) 577, 623 (sh) nm.
4.3.9. Small-scale imidation procedure using imida-
zole/mesitylene/Zn(OAc)2·2H2O, exemplified for 1,6,9-
tris(4-tert-butylphenoxy)-N-(2,6-diisopropylphenyl)peryl-
ene-3,4-dicarboximide (13b). Following a procedure
modified from that of Langhals,9 a mixture of 9 (50 mg,
65 mmol), 2,6-diisopropylaniline (247 mL, 1.30 mmol,
20 equiv.) and Zn(OAc)2·2H2O (13 mg, 59 mmol) in
imidazole (260 mg) and mesitylene (0.8 mL) was stirred
at 1308C. After 19 h, the reaction mixture was cooled to
room temperature and 2N aqueous HCl was added. The
aqueous phase was extracted with CH2Cl2. The CH2Cl2
4.3.11. Preparative-scale imidation procedure using
imidazole/mesitylene/Zn(OAc)2·2H2O, exemplified for
1,6,9-tris(4-tert-butylphenoxy)-N-[2,6-diisopropyl-4-[2-
(triisopropylsilyl)ethynyl]phenyl]-3,4-perylenedicarb-
oximide (13d). Following a procedure modified from that
of Langhals,9 a mixture of 9 (1.00 g, 1.30 mmol), 12d
(9.32 g, 26.1 mmol) and Zn(OAc)2·2H2O (280 mg,
1.28 mmol) in imidazole (5.2 g) and mesitylene (16 mL)

1204
K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
was stirred at 1308C. After 22 h, Zn(OAc)2·2H2O (280 mg,
1.28 mmol) was added. After 14 h (total 36 h), the reaction
mixture was cooled to room temperature and extracted with
CH2Cl2. The organic phase was washed with 2N aqueous
HCl and water, dried (Na2SO4), and concentrated. TLC
analysis [silica, CH2Cl2/hexanes (1:1)] showed the presence
of the title compound (Rf¼0.70, magenta), unreacted 12d
TBAF (694 mL, 0.694 mmol, 1.0 M solution in THF) in
THF (30 mL) at room temperature for 30 min. The reaction
mixture was extracted with CH2Cl2 and the organic phase
was washed with saturated NaHCO3 and water, dried over
Na2SO4, then concentrated. TLC analysis [CH2Cl2/hexanes
(1:1)] showed the title compound (Rf¼0.61, magenta) and a
small amount of byproduct (Rf¼0.50, purple). The resulting
residue was dissolved in toluene/hexanes [100 mL, (1:1)]
and vacuum filtered through a pad of silica [9.5£6.0 cm,
swelled with toluene/hexanes (1:1)] on a fritted glass filter.
A byproduct was removed by eluting with toluene/hexanes
[1.5 L, (1:1)] and the desired product was eluted with
toluene/hexanes [2.0 L, (3:2)]. The product fractions were
combined and concentrated. The resulting solid was
triturated with methanol, affording a magenta solid
(441 mg, 88%). Characterization data were identical to
those in the literature.7
(Rf¼0.55, colorless),
a small amount of byproduct
(Rf¼0.32, colorless), and a small amount of starting material
9 (Rf¼0.29, purple). The residue was diluted with CH2Cl2/
hexanes [100 mL (1:4)] and vacuum filtered through a pad
of silica [9.5£6.0 cm, swelled with CH2Cl2/hexanes (1:4)]
on a fritted glass filter. The byproduct was removed by
eluting with CH2Cl2/hexanes [1.0 L, (1:4), fraction 1] and
the desired product was eluted with CH2Cl2/hexanes [1.0 L,
(1:4), fraction 2], then the mixture of the desired compound
and excess 12d was eluted with CH2Cl2/hexanes [1.0 L,
(1:2), fraction 3]. Fractions 2 and 3 were combined and
concentrated to dryness. The solid was triturated with
methanol followed by filtration, affording a magenta solid
4.3.14. 3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)peryl-
ene-3,4-dicarboximido]-3,5-disopropylphenyl]ethynyl]-
benzaldehyde (20). Following a standard procedure,20
a
1
(687 mg, 48%): mp .2308C; H NMR d 1.12–1.15 (m,
33H), 1.32 (s, 9H), 1.337 (s, 9H), 1.342 (s, 9H), 2.64–2.73
(m, 2H), 6.88 (d, J¼8.8 Hz, 1H), 7.00 (d, J¼8.8 Hz, 2H),
7.05–7.10 (m, 4H), 7.35–7.43 (m, 8H), 7.60–7.66 (m, 1H),
8.30 (s, 1H), 8.33 (s, 1H), 8.47 (d, J¼8.1 Hz, 1H), 9.23 (d,
J¼8.8 Hz, 1H), 9.43 (d, J¼7.3 Hz, 1H); 13C NMR d 11.5,
18.9, 24.0, 29.2, 31.7, 34.6, 107.7, 111.8, 118.2, 118.4,
120.0, 120.5, 121.5, 122.3, 123.8, 124.5, 124.7, 125.1,
125.3, 126.0, 126.8, 127.1, 127.3, 127.9, 128.0, 128.1,
128.3, 130.0, 130.1, 131.0, 131.8, 146.1, 147.1, 147.2,
152.6, 153.4, 153.6, 156.3, 163.3; MALDI-MS (dithranol)
obsd 1105.3 [Mþ]; FAB-MS obsd 1105.6045, calcd
1105.6041 (C75H83NO5Si); labs (log 1) 415 (3.9), 536
(4.6) nm; lem (lex¼500 nm) 576, 622 (sh) nm. The filtrate
generated from trituration with methanol was concentrated
and dried in vacuo followed by bulb-to-bulb distillation
(1708C, 0.01 mm Hg), affording 12d as a faint orange oil
(5.04 g, 54% recovery).
mixture of 13c (100 mg, 95.0 mmol), 3,5-diethynylbenz-
aldehyde (19, 6.2 mg, 40 mmol), Pd2(dba)3 (8.7 mg,
9.5 mmol), and P(o-tol)3 (23 mg, 76 mmol) in toluene/
triethylamine [8.0 mL (5:1)] was stirred under argon at
408C. After 2 h, the reaction mixture was loaded onto a
silica column and eluted with toluene followed by tri-
turation with methanol, affording a magenta solid (34 mg,
42%). Characterization data were identical to those in the
literature.20
4.3.15. 3,5-Bis[2-[4-[9-(4-tert-butylphenoxy)perylene-
3,4-dicarboximido]-3,5-diisopropylphenyl]ethynyl]-
phenyl]benzaldehyde (21). Following a slightly modified
procedure,20 a mixture of 5 (232 mg, 355 mmol), 3,5-di-
bromobenzaldehyde (18, 39.0 mg, 148 mmol), Pd2(dba)3
(27.0 mg, 29.7 mmol), and P(o-tol)3 (54.0 mg, 178 mmol) in
toluene/triethylamine [25 mL (10:1)] was stirred at 608C
under argon. After 3 h, another identical batch of catalyst
was added. After 18 h, the mixture was cooled and passed
through a silica column [CHCl3/ethyl acetate (9:1)]. Two
column chromatography procedures [silica, CHCl3/ethyl
acetate (95:5) and (98:2)] afforded a red solid (74.0 mg,
4.3.12. 1,6,9-Tris(4-tert-butylphenoxy)perylene-3,4-
dicarboxylic anhydride (9): conversion from 13a. Fol-
lowing a standard procedure,9,14 a mixture of 13a (500 mg,
580 mmol) and KOH (1.66 g, 29.6 mmol) in 2-methyl-2-
propanol (35 mL) was refluxed for 2 h. The resulting hot
solution was poured into acetic acid (70 mL) and the
reaction mixture was vigorously stirred for 5 min. Water
(100 mL) was added and the precipitate formed was
collected by filtration. The crude solid was washed with
water and a small amount of methanol (,5 mL). After
drying in vacuo, the solid was dissolved in CH2Cl2/hexanes
[10 mL (1:3)] and vacuum filtered through a pad of silica
(6.0£6.0 cm, swelled with hexanes) on a fritted glass filter.
A byproduct was removed by eluting with CH2Cl2/hexanes
(2:3), then the desired product was obtained by elution with
CH2Cl2/hexanes (2:1). The collected fractions were con-
centrated to dryness and the resulting solid was triturated
with methanol, affording a deep-purple solid (398 mg,
90%). Characterization data were identical to those
described above.
1
35%): mp .2308C; H NMR d 1.22 (d, J¼6.6 Hz, 24H),
1.38 (s, 18H), 2.74–2.81 (m, 4H), 6.99 (d, J¼8.8 Hz, 2H),
7.14 (d, J¼8.8 Hz, 4H), 7.48 (d, J¼8.8 Hz, 4H), 7.54 (m,
4H), 7.71–7.76 (m, 2H), 8.05 (m, 3H), 8.35 (d, J¼8.1 Hz,
2H), 8.39 (d, J¼8.8 Hz, 2H), 8.49 (d, J¼8.1 Hz, 2H), 8.51
(d, J¼7.3 Hz, 2H), 8.60 (d, J¼7.3 Hz, 2H), 8.65 (d, J¼
8.1 Hz, 2H), 8.69 (d, J¼8.1 Hz, 2H), 10.07 (s, 1H); MALDI-
MS (dithranol) obsd 1409.4 [Mþ], calcd avg mass 1409.7
(C99H80N2O7); labs 510 nm; lem (lex¼510 nm) 570, 614,
671 (sh) nm.
4.3.16. 3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)peryl-
ene-3,4-dicarboximido]phenyl]ethynyl]benzaldehyde
(22). Following a standard procedure,20 a mixture of
13a (700 mg, 864 mmol), 3,5-dibromobenzaldehyde (18,
95.0 mg, 360 mmol), Pd2(dba)3 (33.0 mg, 36.0 mmol), PPh3
(57.0 mg, 217 mmol), and CuI (17.0 mg, 89.2 mmol) in
toluene/triethylamine [72 mL (5:1)] was stirred under argon
at 508C. After 3 h, another identical batch of catalyst was
added. After 20 h, the reaction mixture was cooled to room
4.3.13. 1,6,9-Tris(4-tert-butylphenoxy)-N-(2,6-diisopro-
pyl-4-ethynylphenyl)-3,4-perylenedicarboximide (4). A
sample of 13d (640 mg, 0.578 mmol) was treated with

K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1205
temperature and then passed through a silica column
[CHCl3/hexanes (4:1)]. The resulting residue was further
purified by preparative SEC (THF) followed by column
chromatography [silica, CHCl3/hexanes (9:1)] to yield a
After 30 min, DDQ (123 mg, 542 mmol) was added and the
mixture was stirred at room temperature for 1 h. Triethyl-
amine was added to the reaction mixture and the resulting
mixture was filtered through a silica column [CH2Cl2/
hexanes (2:1)]. The resulting residue was dissolved in
CH2Cl2 (40 mL) and the mixture was treated with a solu-
tion of Zn(OAc)2·2H2O (201 mg, 917 mmol) in methanol
(10 mL) at room temperature. After 15 h, the mixture was
washed with water, dried (Na2SO4), then chromatographed
[silica, CH2Cl2/hexanes (2:1)]. The desired fraction was
collected and concentrated. The resulting solid was treated
with methanol and the suspension was sonicated for
1
magenta solid (457 mg, 69%): H NMR d 1.31 (s, 18H),
1.34 (s, 18H), 1.35 (s, 18H), 6.85 (d, J¼8.8 Hz, 2H), 7.00 (d,
J¼8.8 Hz, 4H), 7.06 (d, J¼8.8 Hz, 4H), 7.10 (d, J¼8.8 Hz,
4H), 7.27 (d, J¼8.8 Hz, 4H), 7.36 (d, J¼8.8 Hz, 4H), 7.40–
7.43 (m, 8H), 7.57–7.62 (m, 4H), 7.64 (d, J¼8.8 Hz, 4H),
7.91–7.96 (m, 3H), 8.18 (s, 2H), 8.21 (s, 2H), 8.45 (d,
J¼8.4 Hz, 2H), 9.20 (d, J¼8.8 Hz, 2H), 9.41 (d, J¼8.0 Hz,
2H), 9.98 (s, 1H); 13C NMR d 29.4, 29.7, 31.43, 31.45, 31.5,
34.37, 34.41, 34.44, 87.8, 91.0, 111.5, 118.4, 118.6, 119.8,
119.9, 120.8, 121.9, 122.7, 122.8, 124.0, 124.2, 124.7,
125.6, 126.4, 126.9, 127.07, 127.14, 127.3, 127.5, 127.6,
129.0, 129.7, 129.8, 130.4, 131.2, 132.0, 132.4, 135.5,
136.5, 139.5, 147.0, 147.2, 147.5, 152.6, 153.4, 155.9,
163.1, 190.7; MALDI-MS (POPOP) obsd 1834.3 [Mþ],
calcd avg mass 1834.2 (C127H104N2O12); labs 415, 533; lem
(lex¼420 nm) 575, 625 (sh) nm.
1
10–20 s. Filtration afforded a red solid (45 mg, 10%): H
NMR d 1.28 (s, 18H), 1.30 (s, 18H), 1.34 (s, 18H), 1.84 (s,
6H), 2.64 (s, 3H), 3.31 (s, 1H), 6.89 (d, J¼9.2 Hz, 2H), 7.00
(d, J¼8.4 Hz, 4H), 7.05–7.10 (m, 8H), 7.26–7.29 (m, 6H),
7.35 (d, J¼8.8 Hz, 4H), 7.40 (d, J¼8.8 Hz, 4H), 7.41 (d,
J¼8.8 Hz, 4H), 7.58–7.65 (m, 2H), 7.68 (d, J¼8.4 Hz, 4H),
7.84–7.93 (m, 4H), 8.05 (d, J¼8.0 Hz, 2H), 8.15 (d, J¼
8.8 Hz, 2H), 8.18–8.19 (m, 1H), 8.22 (s, 2H), 8.24 (s, 2H),
8.37–8.38 (m, 2H), 8.47 (d, J¼8.4 Hz, 2H), 8.81 (d, J¼
4.8 Hz, 2H), 8.87 (d, J¼4.4 Hz, 2H), 8.91–8.92 (m, 2H),
8.99 (d, J¼4.8 Hz, 2H), 9.25 (d, J¼8.8 Hz, 2H), 9.45 (d, J¼
8.4 Hz, 2H); MALDI-MS (dithranol) obsd 2597.2 [Mþ],
calcd avg mass 2598.2 (C169H131IN6O10Zn); labs 427
(fwhm¼13 nm), 535 nm; lem (lex¼540 nm) 598, 646 nm.
4.3.17. 5-[3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)-
perylene-3,4-dicarboximido]phenyl]ethynyl]phenyl]di-
pyrromethane (23). Following a standard procedure29 with
slight modification,21 a solution of 22 (500 mg, 273 mmol)
in CH2Cl2 (2.7 mL) was treated with pyrrole (8.0 mL,
0.11 mol) followed by TFA (2.1 mL, 27 mmol). The mixture
was stirred at room temperature. After 15 min, triethylamine
(2 mL) and CH2Cl2 (20 mL) were added. The reaction
mixture was washed with brine, dried over Na2SO4 and
purified by column chromatography (silica, CHCl3),
4.3.19. 5-[3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)-
perylene-3,4-dicarboximido]phenyl]ethynyl]phenyl]-10,
20-bis(4-ethynylphenyl)-15-mesitylporphinatozinc(II)
(17). Following a standard procedure28 with improved acid
catalysis conditions,31 a sample of 25 (54.0 mg, 103 mmol)
was reduced with NaBH4 (78.0 mg, 2.05 mmol) in
THF/methanol [5 mL (10:1)]. The resulting dipyrro-
methane–dicarbinol (25-diol) was reacted with 23
(200 mg, 103 mmol) in CH2Cl2 (40 mL) in the presence of
Yb(OTf)3 (83.0 mg, 134 mmol) at room temperature. After
20 min, the reaction mixture was treated with DDQ
(70.0 mg, 308 mmol) and stirred for 1 h. Triethylamine
was then added and the mixture was filtered through a silica
column [CH2Cl2/hexanes (2:1)]. The resulting residue was
dissolved in CHCl3 (20 mL) and the mixture was treated
with a solution of Zn(OAc)2·2H2O (113 mg, 513 mmol) in
methanol (5.0 mL) at room temperature. After 2 h, the
mixture was washed with water, dried (Na2SO4) and
chromatographed [silica, CH2Cl2/hexanes (2:1)] affording
a red solid (30 mg, 31%): 1H NMR d 0.99 (s, 18H), 1.01 (s,
18H), 1.21 (s, 18H), 1.84 (s, 6H), 2.31 (s, 2H), 2.96–2.98
(m, 3H), 6.57 (d, J¼9.2 Hz, 2H), 6.67 (d, J¼8.8 Hz, 4H),
6.72–6.77 (m, 6H), 6.93–7.09 (m, 12H), 7.31 (d, J¼7.6 Hz,
4H), 7.36 (d, J¼7.6 Hz, 4H), 7.50–7.54 (m, 5H), 7.83–7.84
(m, 4H), 7.90 (d, J¼10.0 Hz, 4H), 8.05 (s, 2H), 8.15 (d,
J¼8.0 Hz, 4H), 8.49–8.67 (m, 12H), 8.93 (d, J¼8.8 Hz,
2H), 9.13 (d, J¼7.6 Hz, 2H), 9.68 (s, 2H); MALDI-MS
(dithranol) obsd 2497.5 [(MþH)þ], calcd avg mass 2496.3
(C171H132N6O10Zn); labs 427 (fwhm¼13 nm), 536 nm; lem
(lex¼540 nm) 598, 647 nm.
1
affording a magenta solid (510 mg, 96%): H NMR d 1.32
(s, 18H), 1.34 (s, 18H), 1.35 (s, 18H), 5.48 (s, 1H), 5.95–
5.98 (m, 2H), 6.19 (dd, J 1¼4.4 Hz, J 2¼2.4 Hz, 2H), 6.26
(dd, J 1¼4.4 Hz, J 2¼2.4 Hz, 1H), 6.83 (dd, J 1¼4.4 Hz,
J 2¼2.4 Hz, 1H), 6.89 (d, J¼9.2 Hz, 4H), 7.00 (d, J¼8.8 Hz,
4H), 7.06 (d, J¼9.2 Hz, 4H), 7.09 (d, J¼8.8 Hz, 4H), 7.26
(d, J¼8.8 Hz, 4H), 7.36 (d, J¼8.8 Hz, 4H), 7.39–7.44 (m,
9H), 7.62 (d, J¼8.8 Hz, 4H), 7.64–7.65 (m, 2H), 8.01 (brs,
2H), 8.21 (s, 2H), 8.23 (s, 2H), 8.48 (dd, J 1¼8.0 Hz,
J 2¼1.2 Hz, 2H), 9.25 (d, J¼8.8 Hz, 2H), 9.25 (d, J¼8.8 Hz,
2H), 9.44 (dd, J 1¼8.0 Hz, J 2¼1.2 Hz, 2H); 13C NMR d
29.7, 31.43, 31.45, 31.5, 34.38, 34.41, 34.44, 43.6, 89.2,
89.7, 107.6, 108.6, 111.6, 117.7, 118.4, 118.6, 119.8, 120.0,
120.9, 122.1, 122.8, 123.3, 123.7, 124.1, 124.3, 125.8,
126.5, 126.9, 127.09, 127.15, 127.3, 127.57, 127.63, 128.8,
129.8, 129.9, 130.5, 130.9, 131.3, 131.5, 132.0, 132.4,
133.5, 135.2, 142.8, 147.1, 147.2, 147.5, 152.7, 153.37,
153.40, 153.45, 153.54, 156.0, 163.2; MALDI-MS (dithra-
nol) obsd 1950.7 [Mþ], calcd avg mass 1950.4
(C135H112N4O2); labs 414, 531 nm; lem (lex¼540 nm)
574, 621 (sh) nm.
4.3.18. 5-[3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)-
perylene-3,4-dicarboximido]phenyl]ethynyl]phenyl]-10-
(4-ethynylphenyl)-20-(4-iodophenyl)-15-mesitylporph-
inatozinc(II) (16). Following a standard procedure28 with
improved acid catalysis conditions,31 a sample of 24
(112 mg, 179 mmol) was reduced with NaBH4 (136 mg,
3.60 mmol) in THF/methanol [20 mL (10:1)]. The resulting
dipyrromethane–dicarbinol (24-diol) was condensed with
23 (344 mg, 179 mmol) in CH2Cl2 (7.0 mL) in the presence
of Yb(OTf)3 (145 mg, 234 mmol) at room temperature.
4.3.20. Sonogashira oligomerization of 16. Following a
standard procedure,21 a mixture of 16 (20 mg, 7.7 mmol),
Pd2(dba)3 (1.1 mg, 1.2 mmol) and AsPh3 (2.8 mg, 9.2 mmol)
in toluene/triethylamine [3 mL (5:1)] was stirred under
argon at room temperature for 40 h. The reaction

1206
K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
mixture was heterogeneous. The bis(perylene)porphyrin
precipitate afforded a very dilute solution in THF upon
sonication at room temperature. Due to the low solubility of
the material, further purification and analysis were not
attempted.
Research, US Department of Energy. Mass spectra were
obtained at the Mass Spectrometry Laboratory for Bio-
technology at North Carolina State University. Partial
funding for the Facility was obtained from the North
Carolina Biotechnology Center and the National Science
Foundation.
4.3.21. Glaser oligomerization of 17. Following a standard
procedure,21,37
a mixture of 17 (25 mg, 10 mmol),
Pd(PPh3)2Cl2 (1.4 mg, 2.0 mmol) and CuI (0.38 mg,
2.0 mmol) in toluene/DIEA [4 mL (5:1)] was stirred at
room temperature for 3 h. The reaction mixture appeared to
be slightly opaque suggesting the formation of some
precipitate. Analysis of a reaction sample by SEC indicated
the presence of a considerable amount (about 40%) of high
molecular weight material with little starting monomer and
short oligomers. The reaction mixture was concentrated to
dryness. The resulting residue was dissolved in THF and the
mixture was passed through a preparative SEC column
(THF). The leading band was collected and concentrated
to dryness. The resulting solid was triturated with metha-
nol and then filtered, then the filtered material was triturated
with hexanes and filtered, affording a red solid (8.2 mg,
33%): labs 437, 507, 548; lem (lex¼450 nm) 607, 654 nm.
References
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5. Yang, S. I.; Lammi, R. K.; Prathapan, S.; Miller, M. A.; Seth,
J.; Diers, J. R.; Bocian, D. F.; Lindsey, J. S.; Holten, D.
J. Mater. Chem. 2001, 11, 2420–2430.
1
A H NMR spectrum was collected but the peaks were
quite broad, indicative of aggregation. Due to the low
solubility of the material, further analysis was not
attempted.
6. Kirmaier, C.; Yang, S. I.; Prathapan, S.; Miller, M. A.; Diers,
J. R.; Bocian, D. F.; Lindsey, J. S.; Holten, D. Res. Chem.
Intermed. 2002, 28, 719–740.
4.3.22. 5,15-Bis[3,5-bis[2-[4-[1,6,9-tris(4-tert-butylphen-
oxy)perylene-3,4-dicarboximido]phenyl]ethynyl]phenyl]-
10,20-dimesitylporphinatozinc(II) (27). Following a stan-
dard procedure,20,32 a mixture of 22 (50 mg, 27 mmol) and
26 (7.2 mg, 27 mmol) in CH2Cl2 (2.5 mL) was treated with
TFA (3.7 mL, 48 mmol) at room temperature for 30 min.
DDQ (9.3 mg, 41 mmol) was then added and the reaction
mixture was stirred for 1 h. After triethylamine was added,
the crude mixture was passed through a silica column
[CH2Cl2/hexanes (3:1)]. The resulting porphyrin was
treated with Zn(OAc)2·2H2O (15 mg, 69 mmol) in CHCl3/
methanol [10 mL (4:1)] at room temperature for 12 h. The
reaction mixture was washed with water, dried over Na2SO4
and then chromatographed [silica, CHCl3/hexanes (3:1)].
The desired fraction was concentrated to dryness. Methanol
was added and the suspension was sonicated for 10–20 s.
7. Loewe, R. S.; Tomizaki, K.-Y.; Chevalier, F.; Lindsey, J. S.
J. Porphyrins Phthalocyanines 2003, In press.
8. Gosztola, D.; Niemczyk, M. P.; Svec, W.; Lukas, A. S.;
Wasielewski, M. R. J. Phys. Chem. A 2000, 104, 6545–6551.
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1229–1244.
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1323–1325.
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Mu¨llen, K. J. Mater. Chem. 1998, 8, 61–64.
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´
Verheijen, W.; Vosch, T.; Christ, T.; Basche, T.; Mu¨llen, K.;
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1
Filtration afforded a red solid (5.0 mg, 8.8%): H NMR d
1.29 (s, 36H), 1.32 (s, 36H), 1.34 (s, 36H), 1.84 (s, 12H),
2.64 (s, 6H), 6.90 (d, J¼8.8 Hz, 4H), 6.99 (d, J¼8.8 Hz,
8H), 7.05 (d, J¼8.8 Hz, 8H), 7.08 (d, J¼8.8 Hz, 8H), 7.25–
7.29 (m, 8H), 7.35 (d, J¼8.8 Hz, 8H), 7.39 (d, J¼8.8 Hz,
8H), 7.42 (d, J¼8.8 Hz, 8H), 7.64 (m, 8H), 7.68 (d, J¼
8.4 Hz, 8H), 8.16 (s, 2H), 8.22 (d, J¼7.6 Hz, 8H), 8.39–
8.40 (m, 4H), 8.48 (d, J¼8.8 Hz, 4H), 8.82 (d, J¼4.4 Hz,
4H), 8.93 (d, J¼4.4 Hz, 4H), 9.26 (d, J¼8.8 Hz, 4H), 9.46
(d, J¼8.8 Hz, 4H); MALDI-MS (dithranol) obsd 4212.89
[(MþH)þ], calcd avg mass 4218.41 (C290H236N8O20Zn);
labs 427 (fwhm¼13 nm), 534 nm; lem (lex¼540 nm) 596,
646 nm.
¨
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This research was supported by the Division of Chemical
Sciences, Office of Basic Energy Sciences, Office of Energy

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