5,10-A2B2-Type meso-substituted porphyrinsa- A unique class of porphyrins with a realigned dipole moment

Article abstract of DOI:10.1002/chem.201101934

Current applications in porphyrin chemistry require the use of unsymmetrically substituted porphyrins. Many current industrial interests in optics and biomedicine require systems with either push-pull (electron-donating and -withdrawing groups) or amphiph

Full text of DOI:10.1002/chem.201101934

DOI: 10.1002/chem.201101934
5,10-A2B2-Type meso-Substituted Porphyrins—A Unique Class of Porphyrins
with a Realigned Dipole Moment
Mathias O. Senge,*[a] Claudia Ryppa,[b] Marijana Fazekas,[a] Monika Zawadzka,[a] and
Katja Dahms[a]
Abstract: Current applications in por-
phyrin chemistry require the use of un-
symmetrically substituted porphyrins.
Many current industrial interests in
optics and biomedicine require systems
with either push–pull (electron-donat-
ing and -withdrawing groups) or am-
phiphilic systems (hydrophobic and hy-
drophilic groups). In this context we
present the class of 5,10-A2B2-type por-
phyrins for which two different sub-
stituents are positioned in diagonally
opposite meso positions. Thus, the in-
tramolecular dipole moment in these
tetrapyrroles is positioned along a b–b
vector passing through two pyrrole
rings. This is opposite to the situation
of the frequently used 5,15-A2BC por-
phyrins for which the dipole moment is
oriented along a meso–meso axis. We
have elaborated syntheses of the 5,10-
A2B2 porphyrins by using transition-
metal-catalyzed transformations of
5,10-A2 porphyrins or direct substitu-
tions reactions thereof; this gives the
target molecules in 22–77% overall
yields. The compounds exhibit interest-
ing structural, spectroscopic, and opti-
cal features and can serve as building
blocks for new porphyrin arrays and
applications.
Keywords: macrocycles · nitrogen
heterocycles
· nonlinear optics ·
porphyrinoids · tetrapyrroles
Introduction
relates to the various regioisomers of meso-substituted por-
phyrins with different residues at the methine bridges.[3]
Figure 1 illustrates the constitution of selected members of
the porphyrin “alphabet soup”.[4] Going back only about a
decade, most of the less symmetrical compounds in this
series were either unknown or had been prepared merely
through mixed condensations in minuscule yields. In practi-
cal terms only the symmetric 5,15-A2 (4) and 5,10,15,20-A4-
type (6) systems could be prepared with ease. Especially the
A- (2) and 5,10-A2-type (3) porphyrins remained almost un-
explored white specks on the porphyrin landscape. The un-
derlying problem is the propensity of pyrrole compounds to
Porphyrins are important natural products and industrially
relevant dyes. Although their basic structure and chemistry
has been known now for almost a century, research into
their chemistry and technical and biomedical uses continues
apace. Indeed, the last quarter of a century has seen an
almost explosive growth of new porphyrinoid, pyrrole-based
chromophores. After the landmark discovery of porphycene
as a C-skeleton isomer of porphyrin by Vogel[1] and the cal-
ixphyrins[2] related to Baeyerꢀs “Azetonpyrrol”[2b] a whole
cornucopia of expanded, contracted, and isomeric porphy-
rins, and cyclopyrroles have been, and continue to be, dis-
covered.[2c,d] In light of this quest for ever more elaborate
porphyrinoid systems, it might come as a surprise to the
nonspecialist that many important classes of the chemically
simpler, “true” porphyrins, that is, 18p-aromatic tetrapyrrol-
ic systems have remained elusive until recently.
Especially the group of the so-called Ax- and ABCD-type
porphyrins contained several missing links. This terminology
[a] Prof. Dr. M. O. Senge, M. Fazekas, M. Zawadzka, Dr. K. Dahms
SFI Tetrapyrrole Laboratory, School of Chemistry
Trinity College Dublin, Dublin 2 (Ireland)
Fax : (+353)1-896-8536
E-mail: sengem@tcd.ie
[b] Dr. C. Ryppa
Institut fꢁr Chemie, Universitꢂt Potsdam
Karl-Liebknecht Str. 24-25
14476 Golm (Germany)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201101934.
Figure 1. Selected Ax- and ABCD-type porphyrins.
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FULL PAPER
undergo acid-catalyzed scrambling reactions.[5] This negated
many total-synthesis approaches and even made it problem-
atic to use preformed building blocks, such as dipyrro-
methanes, for [2+2] or [3+1] condensation reactions. The
only alternative at that time was the use of mixed (alde-
hyde+pyrrole) condensation reactions. Nevertheless, the re-
quired chromatographic workup and acid instability of cer-
tain groups made this prohibitive for, for example, the
ABCD-type systems (10).
In the meantime flexible total-synthesis routes have been
developed for many of these systems by Lindseyꢀs group
and judicious choice of the ABCD residues, their kinetic sta-
bility, steric hindrance, and the sequence of use of the indi-
vidual building blocks allows the large-scale preparation of
many, but not all desired compounds.[6] In parallel we devel-
oped porphyrin syntheses based on the stepwise introduc-
tion of functional groups into preformed macrocycles, that
is, through functionalization reactions. This goes back to our
initial observation that porphyrins can be substituted in high
yield at the meso positions with organolithium reagents,[7]
and by now has evolved to a strategy that utilized various
organometallic reactions for the stepwise transformation of
unsubstituted porphyrins (2, A=H)!A-!AB-!ABC-!
ABCD-type porphyrins.[4,8]
hance optical effects. Thus, contemporary studies habitually
employ 5,15-A2BC porphyrins (8), for which B and C are
used for macrocycle diversification.
Porphyrins of type 8 require a stepwise functionalization
or a total synthesis.[8] Whereas the precursor 5,15-A2 por-
phyrins (4) are easily obtained in high yields.[15] Introduction
of the two different meso substituents B and C requires first
an appropriate monofunctionalization for the introduction
ꢀ
of B (e.g., monobromination and then C C coupling) and
then introduction of C; alternatively a one-pot reaction with
R1Li/R2I is possible.[7b,f] In a fundamental sense this yields
porphyrins with an intramolecular dipole moment aligned
along a 5,15 meso–meso axis (Figure 2, 8). The 5,10-A2B2-
Figure 2. Orientation of the intramolecular dipole moment in 5,15-A2BC-
and 5,10-A2B2-type porphyrins.
Next to access to porphine,[9] this strategy required access
to the monosubstituted porphyrins (2) and appropriate syn-
thetic routes were developed by us based on condensation
and substitution reactions.[10] Logical construction of the
ABCD-type systems (10) through stepwise functionalization
also required a means to introduce a second meso substitu-
ent in a neighboring meso position, that is, a way to generate
the 5,10-regioisomers. Of the two possibilities, use of an ap-
propriate precursor, for example, reaction of tripyrrane[11a]
with pyrrole and aldehyde, or exploitation of the regioselec-
tivity of SNAr reactions in porphyrins,[11b] both could be used
to develop an entry into the 5,10-A2-type systems (3).[10b,12]
Thus, only the 5,10-A2B2 porphyrins remained an unex-
plored entity in the world of meso-substituted porphyrins.
Herein, we present general synthetic routes for the prepara-
tion of these A2B2-type porphyrins and discuss some of their
properties.[13]
type systems are accessible more easily (Scheme 1). They re-
quire no selective monofunctionalization, rather a double
substitution of the “free” 15,20 positions (e.g., unspecific di-
ꢀ
bromination and then C C coupling; see Scheme 2).
Herein, only two different substituents (A and B) are re-
quired to construct unsymmetrical systems. Thus, in the case
of electron-withdrawing/donating groups, porphyrins, for
which the dipole moment passes through the middle of two
opposing b–b units (N···N), will be obtained (Figure 2, 9).
Results and Discussion
Scheme 1. Synthesis of 5,10-A2B2-porphyrins with organolithium reagents.
i) R2Li, THF; ii) H2O; iii) 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ). a) 11: M=NiII, R1 =Ph; 12: M=2H, R1 =4-Me-C6H4; 13: M=
2H, R1 =iBu; 14: M=2H, R1 =Ph; 15: M=2H, R1 =3-MeO-C6H4; 16:
M=2H, R1 =2,6-DiF-C6H3. b) 17: M=NiII, R1 =Ph, R2 =R3 =hexyl
(58%); 18: M=2H, R1 =4-Me-C6H4, R2 =hexyl, R3 =H (18%); 19: M=
2H, R1 =4-Me-C6H4, R2 =R3 =hexyl (22%); 20: M=2H, R1 =iBu, R2 =
R3 =hexyl (26%); 21: M=2H, R1 =4-Me-C6H4, R2 =R3 =nBu (31%);
22: M=2H, R1 =Ph, R2 =nBu, R3 =H (26%); 23: M=2H, R1 =4-Me-
C6H4, R2 =R3 =4-Me2N-C6H4 (71%); 24: M=2H, R1 =4-Me-C6H4, R2 =
R3 =4-HO-C6H4 (57%); 25: M=2H, R1 =3-MeO-C6H4, R2 =R3 =4-
Me2N-C6H4 (32%); 26: M=2H, R1 =3-MeO-C6H4, R2 =4-Me2N-C6H4,
R3 =H (5%); 27: M=2H, R1 =4-Me-C6H4, R2 =R3 =4-ethynyl-C6H4
(31%); 28: M=2H, R1 =2,6-DiF-C6H4, R2 =R3 =4-ethynyl-C6H4 (25%).
Synthetic rational and brief review of the literature: Current
application developments indicate a considerable demand
for unsymmetrically substituted porphyrins. Examples for
this are amphiphilic porphyrins in photodynamic cancer
therapy (PDT),[14a] synthons for crystal engineering and
supramolecular chemistry,[14b] push–pull systems for biomim-
etic studies on electron transfer,[14c] and uses in optics, espe-
cially in nonlinear optics (NLO).[14d] Unsymmetrical substi-
tution is used to either position donor/acceptor residues in a
manner suitable for the desired interaction or to yield sys-
tems with a strong intermolecular dipole moment to en-
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M. O. Senge et al.
Synthesis through RLi reactions: Based on our earlier expe-
rience with the use of organolithium reagents for the meso
functionalization of porphyrins,[7] it was logical to apply
these for the current problem as well. For initial experi-
ments we used nickel(II)porphyrin 11, which typically shows
good reactivity with RLi. To achieve full substitution of
both 15,20 meso positions we used 6 equivalents of hexyl-
lithium. Indeed, the target compound 17 was obtained in
58%. The different reactivity of free base and metallo por-
phyrins became evident when a similar experiment was per-
formed with 12. Here, a low yield of the monosubstituted
porphyrin 18, that is, a 5,10-A2B system, was obtained. Full
disubstitution to 19 was only achieved when the number of
hexyllithium equivalents was raised to 10. A similar reactivi-
ty was found for 13, which could be transformed into 20 in
26%. The use of nBuLi and reaction with 12 to give 21 did
not improve the yield significantly, whereas the use of
20 equivalents of nBuLi with 14 in the presence of
N,N,N’,N’-tetramethylethylenediamine (TMEDA) only gave
the A2B porphyrin 22.
Next, we tried to introduce residues with functional
groups by using the same methodology through in situ gen-
eration of organolithium reagents. For example, reaction of
12 with 4-(N,N-dimethylamino)phenyllithium gave 23 in
71% yield. However, the reaction is somewhat inefficient as
it requires 100 equivalents of RLi. Likewise, the p-hydroxy-
phenyl derivative 24 could be prepared in good yield. Reac-
tion of the methoxyphenylporphyrin 15 gave 25, accompa-
nied by a small amount of 26. Similarly, the p-phenylethynyl
group could be introduced into the tolylporphyrin 12 to
yield 27. Finally, the free-base porphyrin 16 was prepared
through a condensation approach in 5% yield and reacted
with p-phenylethynyllithium to give 28. We also attempted
the introduction of stronger electron-withdrawing groups
through similar reactions. However, a reaction of 12 by
using nBuLi/p-bromobenzonitrile (ꢀ1008C) only gave the
butylated product 21. No reaction was observed with 1-
bromo-4-nitrobenzene/nBuLi and only starting material was
recovered.
Scheme 2. Synthesis of 5,10-A2B2-porphyrins by using Heck reactions.
i) N-bromosuccinimide (NBS), pyridine, CHCl3; ii) ZnO, CH2Cl2, tri-
fluoroacetic acid (TFA) or NiACTHNUTGRENN(UG acac)2, toluene, D; iii) PdACHTUNGTREN(NUGN OAc)2, NaOAc,
PPh3, DMF, D.
5,10-Disubstitued porphyrins were first reported by
Longo, but not characterized.[16a] In the early 21st century,
examples for condensation reactions,[16b] total syntheses,[16c]
and N-confused derivatives[16d] were reported. This was then
followed by the more general methods described above for
porphyrins[10b,12] and calixphyrins.[16e] This opened the possi-
bility to use the 5,10-A2 porphyrins as simple starting mate-
rials for the synthesis of 5,10-A2B2 systems as outlined
above. A few 5,10-A2B2 compounds have been reported
before; however, all were prepared in low yields through
statistical condensation methods by using pyrroles, dipyrro-
methanes, or tripyrranes with the usual attendant problems
of tedious chromatographic separation, scrambling, and
other limitations.[17] The only exception is Lindseyꢀs elegant
study on the development of total syntheses by using diacyl-
dipyrromethanes. This method was successfully used to pre-
pare some compounds with aryl substitutents.[6a]
Synthesis through Heck reactions: To expand the scope of
these compounds we next turned our attention to the use of
Pd-catalyzed reactions. Many of these have now been ap-
plied to porphyrin chemistry.[4] The Heck reaction[18a] was in-
itially applied for the b substitution of porphyrins[18b] and we
were interested in preparing meso-vinyl-acceptor-substituted
porphyrins.
The Heck reaction requires a bromo-substituted coupling
partner and thus preparation of bromoporphyrins was the
first step. DiMagno et al.[19] had shown that 5,15-A2 porphy-
rins can easily be brominated with NBS in both meso posi-
tions and the same conditions could be applied straightfor-
wardly to the 5,10-A2-type systems. Ditolylporphyrin, used
for exploration of this reaction, was brominated to 29. To
prevent the incorporation of Pd from the catalysts we trans-
formed 29 into the respective zinc(II) 30 and nickel(II)por-
phyrins 31. First we reacted zinc(II) porphyrin 30 with butyl
Based on the current state of the art in porphyrin func-
tionalization reactions there are several methods for the in-
troduction of the B residue into an A2 porphyrin. The ma-
jority of them employs organometallic reagents and is dis-
cussed in subsequent sections.
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Porphyrins with Realigned Dipole Moment
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Table 1. Synthesis of 5,10-A2B2-porphyrins by using Suzuki reactions.[a]
acrylate. Heating at 1208C for 24 h gave the desired {(all-
E)-5,10-bis(4-(2-butoxycarbonylethenyl)-15,20-di(p-tolylpor-
phyrinato}zinc(II) 32 as the sole product in 64%. Similarly,
reaction with a methyl vinylketone gave 33. The E configu-
ration is clearly evidenced by the NMR coupling constant of
16 Hz. Reaction of zinc(II) complex 30 with nitrostyrene
gave the analogous porphyrin 34 in good yield. Nickel(II)
complex 31 is less reactive and reaction with nitrostyrene
gave 35 in much lower yield (Scheme 2).
R1
R2
Yield [%]
43
44
45
52
47
47
Synthesis through Suzuki reactions: Next, we focused on ap-
plications of the Suzuki reaction for the task at hand. Suzuki
reactions have been very fruitfully applied to porphyrins
and offer the advantage that no prior metallation is necessa-
ry.[20] Again, bromoporphyrins are required as coupling part-
ners and, in addition to the ones mentioned above, a few
more (36–40, Scheme 3) were synthesized to gain access to a
broader range of A/B substituent systems. Likewise, two
new 5,10-A2 porphyrins (41, 42) were prepared by using
condensations reactions.
46
47
30
47
48
49
50
30
29
43
51
52
53
30
47
56
Scheme 3. Structures of compounds 36–42. a) 36: R=Ph (70%); 37: R=
3-MeO-C6H4 (74%); 38: R=2,6-DiF-C6H3 (58%); 39: R=pentyl (60%);
40: R=hexyl (50%). b) 41: R=4-Br-C6H4 (4%); 42: R=3,4,5-TriF-C6H2
(1%).
54
55
56
30
28
22
By now optimized catalyst/base systems have been estab-
lished for Suzuki reactions with 5,15-A2 systems.[20d] These
could be easily applied for the modification of 5,10-A2 por-
phyrins. As shown in Table 1 a large set of compounds could
be prepared with [PdACHTNUTRGNEUNG(PPh3)4] as palladium catalyst and
K3PO4 as a base. Yields varied from 22 to 59%, both aryl
and alkyl halgenoporphrins could be used, and reaction
times from 7 to 13 h. For example, the bromotolylporphyrin
29 was reacted with 4-methoxycarbonylphenyl boronic acid
for 7 h and gave 43 in 52% yield. The best yield for this re-
agent was obtained for the pentylporphyrin derivative 57.
The reactivity of 4-cyanophenyl boronic acid towards aryl
and alkyl haloporphyrins was investigated as well. The best
results of 47% each were obtained for 44 and (3-methoxy-
phenyl)porphyrin 52. Alkyl haloporphyrins, for example,
5,10-dibromo-15,20-dipentylporphyrin or 5,10-dibromo-
15,20-dihexylporphyrin gave the corresponding products 58
and 61, respectively, in 40% yield. Even lower yields were
obtained for porphyrins 48 and 49, materials synthesized
from 5,10-dibromo-15,20-diphenylporphyrin 70.
57
58
59
60
61
61
pentyl
pentyl
pentyl
pentyl
pentyl
pentyl
57
40
47
34
40
59
[a] Reaction conditions: boronic acid or ester, K3PO4, PdACHTNURGTNE(UNG PPh3)4, THF, D.
required longer reaction times than the 4-nitrophenyl boron-
ic acid and gave lower yield. This was not the case for the 3-
cyanophenyl versus 4-cyanophenyl reagent. Reactions with
the electron-poor 2,3-difluorophenylporphyrins proceeded
Introduction of the nitrophenyl residue proceed well with
good yields, for example, for compounds 45, 50, 53 and the
alkylporphyrins 59 and 62. The 3-nitrophenyl boronic acid
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M. O. Senge et al.
poorly with yields ranging from 22 to 30%. Clearly, the
Suzuki reaction provides convenient access to various 5,10-
A2B2-type porphyrins. Still, some scope for optimization
exists. A number of the free-base porphyrins prepared from
the reactions described above, were converted into the re-
spective zinc(II)porphyrins for comparative photophysical
analyses. The metalloporphyrins 63–68 were obtained
through standard reactions in good yields (Table 2).
Scheme 4. Synthesis of the diformylporphyrin 70. i) DMF, POCl3, di-
chloroethane, 50–908C.
Table 2. Metalloporphyrins 63–68.
R1
R2
Yield [%]
63
64
65
81
81
72
66
67
68
Br
90
72
81
Figure 3. View of the molecular structure of the crystal of 29. Hydrogen
atoms have been removed for clarity and thermal ellipsoids show 50%
occupancy.
the structural properties are similar to those of 5,15-A2B2-
and A4-type porphyrins. There is no evidence for core elon-
gation or other changes to the core structure. For example,
the core size (average N…Ct distance; Ct=center) is 2.064 ꢄ
and similar to that of 5,10,15,20-tetraphenylporphyrin
(TPP).[24] Similarly, the bond lengths and angles of the tetra-
pyrrole framework are in line with normal porphyrin sys-
tems.[25] The packing of the molecules (not shown) is charac-
terized by the formation of weak p–p aggregates in a head-
to-tail fashion.[25]
Functionalization reactions: The target systems can also be
prepared through simple functionalization reactions. Exam-
ples for this are the partial reduction of nitro groups in a tet-
ranitrophenylporphyrin.[21a] Perhaps not elegant in synthetic
chemistry terms, such strategies offer a quick entry into vari-
ous systems and have recently been used to generate 5,10-
type precursors for Huisgen CuI coupling chemistry.[21b]
Other, “simple” reactions may be performed as well. For
example, the Vilsmeier formylation[22a] has been used often
for the modification of porphyrins.[22b–d] Under excess condi-
tions, it can be used to diformylate metallo octaethylpor-
phyrins[22c] and 5,15-A2-type porphyrins,[22d] but mostly gives
mixtures of the mono- and diformyl product. In the case of
5,10-A2 porphyrin 69, standard Vilsmeier–Haack formyla-
The conformation of the molecule is nonplanar.[25a,b] The
average deviation of the 24 macrocycle atoms from their
least-squares-plane (D24) is 0.159 ꢄ, slightly less than the
tetragonal form of TPP.[26] The macrocycle exhibits a ruffled
distortion mode, with alternate meso-carbon (Cm) displace-
ments of 0.15–0.34 ꢄ from the 24-macrocycle atom plane. A
detailed normal structural decomposition analysis (NSD)[27]
reveals a more complex situation. The conformation is char-
acterized by almost similarly strong out-of-plane contribu-
tions from sad and ruf distortions (B1u and B2u), a moderate
contribution from doming (A2u), and a minor one from
wave (Egx). With regard to in-plane distortion modes, the
most significant contributor is macrocycle breathing (A1g).
In a first approximation this is similar to the structure of
tion gave the respective 5,10-A2ACTHNUTRGNEUNG(CHO)2-porphyrin 70 in
very good yield (77%) and as the sole product (Scheme 4).
Other possibilities for selective functionalizations (e.g., 41)
are the use of organotin reactions.[23]
Structural studies: To establish some basic structural fea-
tures of the 5,10-A2B2-type porphyrins, a X-ray crystallo-
graphic analysis of compound 29 was performed. The molec-
ular structure of the crystal is shown in Figure 3. Overall,
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Porphyrins with Realigned Dipole Moment
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5,10-diphenylporphyrin,[28] which exhibits less sad distortion
and more wave contribution.
In the past push–pull molecules with a similar orientation
of the intramolecular dipole moment, that is, along the b–b
vector that passes through two pyrrole rings were obtained
through the functionalization of the b position of the por-
phyrin ring, for example, in TPP derivatives.[31] In the well-
studied 5,15-A2BC compounds the push–pull character is
tuned through the B and C substituents. Herein, the dipole
moment is aligned along the 5,15 meso–meso axis. Neverthe-
less, access to these 5,15-A2BC compounds is more complex
in comparison to 5,10-A2B2 as it involves firstly an appropri-
ate monofunctionalization of the 5,15-A2 precursor and sec-
ondly further additional steps for the incorporation of the
third functional group C. In case of 5,10-A2B2 compounds
only two substituent are needed to introduce a dipole
moment; this consequently involves fewer steps and omits
the troublesome monofunctionalization.
The 5,10-A2B2 compounds are candidates for many poten-
tial applications. Inequivalent substituents can be used to
bring about an amphiphilic character of the molecule; this
turns those compounds into drug candidates for PDT appli-
cations. The push–pull character can be tuned through A
and B substituents and makes 5,10-A2B2 porphyrins an inter-
esting group of compounds for electron transfer (ET) stud-
ies and optics, especially NLO. Our preliminary NLO stud-
ies indeed revealed that those compounds exhibit interesting
properties in this area. 5,10-A2B2-type systems can also be
used as crystal engineering synthons to access new supra-
molecular structures. For example, Maeda et al. reported re-
cently on L-shaped porphyrin trimers, for which the assem-
blies exhibited efficient ET. Those compounds were pre-
pared through functionalization of the 5,10-A2B2-dibromi-
nated precursor with appropriate 5,15-A2BC porphyrins.[32]
5,10-A2B2 porphyrins may also serve as new ligand systems,
as was shown recently for the related calixphyrins.[33]
NLO properties: Understanding the nonlinear absorption
(NLA) properties of macrocyclic dyes is important for the
development of related applications. Besides instantaneous
two-photon absorption (TPA), which arise at nonresonant
frequencies and has potential for 3D microfabrication and
multiphoton microscopy, porphyrins exhibit sequential TPA,
that is, reverse saturable absorption (RSA) and saturable
absorption (SA) at resonant or close to resonant wave-
lengths. The latter two processes occur when the absorption
that arises from higher excited state is higher and lower re-
spectively to that of the ground state. RSA has potential for
use in pulse sensors and in optical-limiting devices that pro-
tect sensitive optical components or the human eye from
laser-induced damage. SA finds application for mode lock-
ing, laser pulse compression, and laser amplification.
Our open-aperture Z-scan studies at close-to-resonant
wavelengths revealed that 5,10-A2B2 compounds exhibit an
interesting NLO effect, which has not been observed for
porphyrins in the nanosecond regime before. The com-
pounds exhibit pure RSA response when low laser-energy
inputs were used; this is a standard response commonly ob-
served for macrocyclic dyes under these experimental condi-
tions. However, when the input energy was increased and
the on-focus intensity (I00) reached approximately
0.4 GWcmꢀ2, the RSA response was observed to switch to
SA in the tight focal regime. When the input energy was in-
creased further on and I00 was in the order of about
0.5 GWcmꢀ2, a similar RSA/SA signal was detected, though
with a much more pronounced SA peak. The SA response
within an RSA remained highly symmetrical for all of the
measurements (not shown).[29]
Interestingly, compounds with similar substituents, but in
a 5,15-A2B2 substitution pattern, exhibit a pure RSA re-
sponse both at lower and higher inputs.[30] This clearly dem-
onstrates that the RSA/SA switch is intrinsic to 5,10-A2B2
compounds. The origin of the behavior is not understood at
this stage. Most likely the RSA/SA switch is the result of ab-
sorption arising from higher excited states. Further studies
are necessary to understand the observed switch.
Experimental Section
General methods: Instrumentation and standard techniques is described
elsewhere.[8] NLO studies were carried out with an open-aperture Z-scan
technique.[34] Experimental set-up and sample preparation details can be
found elsewhere.[13]
Starting materials: Tripyrrane,[35] and various 5,10-di(alkyl/aryl)porphy-
rins[10b] were prepared according to published procedures.
General procedure A—condensation method for 5,10-A2 porphyrins: A
three-necked flask was charged with a solution of tripyrrane (1 equiv),
pyrrole (1equiv), and the corresponding aldehyde (2.1 equiv) in dry
CH2Cl2 (1 L). The mixture was shielded from light and stirred under
argon for 30 min. TFA (100%) was added and stirring was continued at
RT for 16 h. This was followed by oxidation with DDQ (4 equiv), stirring
for 60 min, and addition of triethylamine (1 mL). Typically, the reaction
Conclusion
We herein present a conceptionally new class of push–pull
porphyrins, that is, 5,10-A2B2 porphyrins, with the intramo-
lecular dipole moment positioned along the b–b vector pass-
ing through two pyrrole rings. Starting from 5,10-A2 precur-
sors, numerous 5,10-A2B2 compounds with varied push–pull
character can be obtained by using organolithium, palladi-
um-catalyzed cross-coupling or other functionalization reac-
tions. These approaches allow the synthesis in moderate to
good yields and open an avenue for further studies on these
yet poorly explored compounds.
mixture was filtered through
a short silica-gel column, eluted with
CH2Cl2, then the solution was concentrated in vacuo and the residue pu-
rified by column chromatography on silica gel.
General procedure B—reactions with organolithium compounds:
A
250 mL Schlenk flask was charged with the porphyrin (1 equiv) in THF
(50 mL) under argon. The solution was cooled to ꢀ708C for alkyl lithium
reagents or 08C for aryl lithium reagents. The respective LiR compound
was added dropwise over 15 min and the color changed from red to
brown–green. The cold-water bath was removed and the solution was
Chem. Eur. J. 2011, 17, 13562 – 13573
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
13567

M. O. Senge et al.
3
3
ꢀ
stirred for 30 min at RT. A mixture of water (1 mL) in THF (5 mL) was
added and the color changed to green. The mixture was stirred for
15 min and, unless noted otherwise, oxidized with DDQ (5.5 equiv) fol-
lowed by stirring for 30 min. This was accompanied by a color change to
red. The solution was filtered through silica gel (CH2Cl2) and the solvent
removed under reduced pressure. For in situ preparation of RLi reagents
n-butyllithium (2 equiv) was slowly added (ca. 1 h) under an argon at-
mosphere to a 100 mL Schlenk flask charged with a solution of the bro-
mine (1 equiv) in dry diethyl ether (10 mL) at ꢀ788C. The reaction mix-
ture was then warmed up to ꢀ408C and THF was added dropwise until
the aryllithium was formed as a bright pink suspension. Under argon at-
mosphere, a solution of the porphyrin (0.9 equiv) in dry THF (80 mL)
was added rapidly to the vigorously stirred RLi-containing mixture. The
color of the reaction mixture changed from purple to brown within
30 min, subsequently water (5 mL) in dry THF (5 mL) was added for hy-
drolysis. When the mixture had been stirred for 10 min, a solution of 10–
15 equivalents of DDQ in CH2Cl2 was added and the reaction mixture
was stirred for another 60 min at RT.
CH2CH2C4H9), 4.54 (t, J= J=7.8 Hz, 4H, CH2C5H11), 7.66 (m, 6H, Ar
ꢀ
ꢀ
Hm, Ar Hp), 7.97 (m, 4H, Ar Ho), 8.63 (brs, 2H, Hb7,8), 8.73 (AB,
3JH2,H3 =3JH13,H17 =3JH12,H13 =3JH18,H17 =5.1 Hz, 2H,
3JH3,H2 =3JH12,H13 =5.1 Hz, 2H,
b3,12), 9.34 ppm (brs, 2H,
H
b2,13), 9.24 (AB,
b17,18);
H
H
13C NMR (75 MHz, CDCl3, 258C, TMS): d=14.10, 22.65, 30.05, 31.77,
34.20, 37.41, 117.58, 118.20, 126.83, 127.57, 129.51, 129.81, 131.94, 132.22,
133.62, 140.92, 141.66, 141.74, 141.97,142.03 ppm; UV/Vis (CH2Cl2): lmax
(lg e)=416 (5.21), 532 nm (4.06); MS (70 eV, EI, 3508C): m/z (%): 686
(100, [M] +), 615 (89, [MꢀC5H11]+), 544 (50, [Mꢀ2C5H11] +); HRMS:
m/z: calcd for [C44H45N4Ni]: 687.2998 [M+H]+; found: 687.2936.
5,10-(n-Dihexyl)-15,20-bis(4-methylphenyl)porphyrin (19): Compound 12
(79 mg, 0.16 mmol) was reacted with a solution of n-hexyllithium in n-
hexane (2.5m, 0.65 mL, 1.61 mmol, 10 equiv) by following procedure B.
Purification on silica gel (CH2Cl2/n-hexane=1:1, v/v) and recrystalliza-
tion from CH2Cl2/MeOH gave purple crystals (23 mg, 0.03 mmol, 22%).
Rf =0.55 (CH2Cl2/n-hexane=1:1, v/v); m.p. 1728C; 1H NMR (300 MHz,
CDCl3, 258C, TMS): d=ꢀ2.64 (brs, 2H, NH), 0.99 (t, 3J=3J=7.2 Hz,
6H, 6H, C5H10CH3), 1.44 (m, 4H, C4H8CH2CH3), 1.54 (m, 4H,
C3H6CH2C2H5), 1.83 (m, 4H, C2H4CH2C3H7), 2.56 (m, 4H,
General procedure C—bromination of 5,10-A2 porphyrins: A 100 mL
round-bottom flask was charged with the porphyrin (1 equiv) dissolved in
chloroform (50 mL) and pyridine (0.2 mL) and was cooled to 08C. Next,
NBS (2.5 equiv) was added and the solution stirred for 10 min. The color
changed from red to brown–red. The reaction was then quenched
through addition of acetone (4 mL). The solvent was removed under re-
duced pressure, the residue dissolved in CH2Cl2 and filtered through
silica gel (CH2Cl2). The solvent was removed under reduced pressure and
the residue was washed with MeOH and dried.
CH2CH2C4H9), 2.73 (s, 6H, Ar CH3), 4.97 (t, 3J=3J=7.9 Hz, 4H,
ꢀ
3
3
3
3
ꢀ
CH2C5H11), 7.56 (AB, J= J= J= J=7.9 Hz, 4H, Ar Hm), 8.10 (AB,
J= J= J= J=7.9 Hz, 4H, Ar Ho), 8.81 (s, 2H, Hb17,18), 8.92 (AB, 3J=
3
3
3
3
ꢀ
4.9 Hz, 2H, b3,12),
H
b2,13), 9.44 (AB, 3JH3,H2 =3JH12,H13 =4.9 Hz, 2H,
H
9.53 ppm (s, 2H, Hb7,8); 13C NMR (75 MHz, CDCl3, 258C, TMS): d=
14.16, 21.50, 22.75, 30.28, 31.93, 35.65, 38.81, 118.81, 119.81, 127.38, ꢁ128,
ꢁ131, 134.42, 139.47 ppm; UV/Vis (CH2Cl2): lmax (lg e)=419 (4.92), 517
(3.82), 554 (3.61), 595 (3.34), 651 nm (3.45); MS (70 eV, EI): m/z (%):
658 (16 [M]+), 587 (67, [M ꢀC5H11]+), 516 (27, [Mꢀ2C5H11]+), 425 (4,
[Mꢀ2C5H11ꢀC7H7]+), 334 (4, [Mꢀ2 C5H11ꢀ2C7H7]+), 329 (37, [M]2+),
294 (18, [MꢀC5H11]2+), 259 (43, [Mꢀ2C5H11]2+); HRMS: m/z: calcd for
[C46H50N4]: 658.4035 [M]+; found: 658.4014.
General procedure D—insertion of zinc(II): The free-base porphyrin
(1 equiv) and zinc oxide (2–3 equiv) were dissolved in CH2Cl2 (50 mL)
and treated with three to five drops of TFA. After stirring for 10 min the
color changed from green to purple–red. The reaction was followed by
TLC control and the solution filtered through silica gel (CH2Cl2) and the
solvent removed under reduced pressure.
5,10-DiACTHNUGRTENUNG(n-hexyl)-15,20-di(iso-butyl)porphyrin (20): Compound 13 (30 mg,
0.07 mmol) was reacted with a solution of n-hexyllithium in n-hexane
(2.5m, 0.29 mL, 0.71 mmol, 10 equiv) following procedure B. Purification
on silica gel (n-hexane/ethyl acetate=5:1, v/v) and recrystallization from
CH2Cl2/MeOH gave purple crystals (11 mg, 0.02 mmol, 26%). Rf =0.67
(CH2Cl2/n-hexane=2:3, v/v); m.p. 978C; 1H NMR (300 MHz, CDCl3,
258C, TMS): d=ꢀ2.65 (brs, 2H, NH), 0.95 (t, 3J=3J=7.2 Hz, 6H,
General procedure E—Heck reactions:
A 50 mL three-necked flask
equipped with condenser was charged with the zinc(II)porphyrin
a
(10 equiv), sodium acetate (56 equiv), palladium acetate (1 equiv), and
triphenylphosphine (4 equiv) in dry DMF (15 mL) under argon. Next,
the respective olefin was added and the solution heated at 1208C for
24 h. The reaction was followed by TLC control. After completion of the
reaction the solution was cooled to RT mixed with CH2Cl2, washed with
water (50 mL) and dried over Na2SO4. The solvent was removed under
reduced pressure and the residue was dissolved in CH2Cl2. The solution
was filtered through alumina (Brockmann grade III, eluent: CH2Cl2, 1%
triethylamine) and the solvent was removed under reduced pressure.
Final purification involved recrystallization from CH2Cl2/n-hexane.
C5H10CH3), 1.19 (d, 3J=3J=3J=3J=6.7 Hz, 12H, CH2CH
ACHTUNGTRENNUNG
(m, 8H, C3H6ACTHUNGTRENNUNG
CH2CH2C4H9), 2.75 (m, 2H, CH2CHACHTUNTRGNEUNG
(CH3)2), 4.82 (d, J=3J=7.3 Hz, 4H,
3
CH2CHACHTNUGRTNEUNG
(CH3)2), 4.93 (t, 3J=3J=8.0 Hz, 4H, CH2C5H11), 9.46 ppm (m,
8H, Hb); 13C NMR (75 MHz, CDCl3, 258C, TMS): d=14.16, 22.77, 23.33,
30.29, 31.94, 35.58, 36.68, 38.66, 43.76, 117.17, 118.51, ꢁ129 ppm; UV/Vis
(CH2Cl2): lmax (lg e)=418 (4.97), 520 (4.12), 554 (3.99), 599 (3.74),
659 nm (3.83); MS (70 eV, EI): m/z (%): 590 (100, [M]+), 547 (69,
[MꢀC3H7]+), 519 (11, [MꢀC5H11]+), 295 (4, [M]2+); HRMS: m/z: calcd
for [C40H54N4]: 590.4348 [M]+; found: 590.4346.
General procedure F—Suzuki reactions: A Schlenk flask was charged
with K3PO4 (20 equiv) and anhydrous THF (60 mL) under an argon at-
mosphere, then porphyrin (1 equiv), arylboronic acid or arylboronic ester
(10 equiv), and [PdACHTUNGTRENNUNG(PPh3)4] (0.1 equiv) were added. The reaction was
5,10-DiACTHNUGRTENUNG(n-butyl)-15,20-bis(4-methylphenyl)porphyrin (21): By following
heated at reflux for 7–10 h (TLC control) and protected from light. After
completion, the solvent was evaporated and the residue was dissolved in
CH2Cl2. The mixture was washed with saturated NaHCO3, water, and
brine and then dried over Na2SO4. The organic solvent was evaporated
and the crude product was purified by flash chromatography followed by
recrystallization.
procedure B and the details given for 27, reaction of n-butyllithium
(4 mL of 2.5m solution in n-hexane, 10 mmol), a solution of p-bromoben-
zonitrile (0.72 g, 4.0 mmol) in of dry diethyl ether (15 mL) at ꢀ1008C
and compound 12 (50 mg, 0.110 mmol) gave 24 mg (0.034 mmol, 31%),
of the title compound. M.p.>3008C; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d=ꢀ2.67 (s, 2H, NH), 1.17 (t, 3J=7., 7.6 Hz, 6H,
CH2CH2CH2CH3), 2.34 (m, 4H, CH2CH2CH2CH3), 2.57 (m, 4H,
General procedure G—insertion of nickel(II): Porphyrin (1 equiv) and
NiACHTUNGTRENNUNG(acac)2 (1.1 equiv) were dissolved in toluene (20 mL) and heated to
reflux. The progress of the reaction was monitored by TLC. Upon com-
pletion, the solvent was removed in vacuo and the product was isolated
after passage through a plug of silica gel with CH2Cl2 as the eluent.
CH2CH2CH2CH3), 2.76 (s, 6H, Ar CH3), 5.04 (t, 3J=7.6, 8.2 Hz, 4H,
ꢀ
3
CH2CH2CH2CH3), 7.57 (d, J=7.6 Hz, 4H, Ar H), 8.08 (d, 3J=7.6 Hz,
ꢀ
4H, Ar H), 8.78 (s, 2H, Hb), 8.91 (d, 3J=4.7 Hz, 2H, Hb), 9.46 (d, 3J=
ꢀ
4.7 Hz, 2H, Hb), 9.6 ppm (s, 2H, Hb); 13C NMR (63 MHz, CDCl3, 258C,
TMS): d=14.06 21.36, 23.54, 29.55, 35.23, 40.77, 118.66, 119.63, 127.19,
127.27, 134.25 137.02, 139.28 ppm; UV/Vis (CH2Cl2): lmax (lg e)=418
(4.92), 518 (3.56), 555 (3.36), 603 (3.05), 647 nm (3.02); HRMS: m/z:
calcd for [C42H43N4]: 603.3488 [M+H]+; found: 604.3472.
ACHTUNGTRENNUNG[5,10-DiACHTUNGTRENNUNG(n-hexyl)-15,20-diphenylporphyrinato]nickel(II) (17): Compound
11 (37 mg, 0.07 mmol) was reacted with a solution of n-hexyllithium in n-
hexane (2.5m, 0.17 mL, 0.43 mmol, 6 equiv) by following procedure B.
Purification on silica gel (CH2Cl2/n-hexane=1:1, v/v) and recrystalliza-
tion from CH2Cl2/MeOH gave purple crystals (28 mg, 0.04 mmol, 58%).
Rf =0.69 (CH2Cl2/n-hexane=1:1, v/v); m.p. 1678C; 1H NMR (300 MHz,
CDCl3, 258C, TMS): d=0.90 (t, 3J=3J=7.3 Hz, 6H, C5H10CH3), 1.35 (m,
5,10-Bis[4-(N,N-dimethylamino)phenyl]-15,20-bis(4-methylphenyl)por-
phyrin (23): Compound 12 (63 mg, 0.13 mmol) was reacted with 4-(N,N-
dimethylamino)phenyllithium by following procedure B. Purification on
silica gel (CH2Cl2) and recrystallization from CH2Cl2/MeOH gave purple
8H, C3H6ACHTUNGTRENNUNG(CH2)2CH3), 1.59 (m, 4H, C2H4CH2C3H7), 2.29 (m, 4H,
13568
www.chemeurj.org
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 13562 – 13573

Porphyrins with Realigned Dipole Moment
FULL PAPER
crystals (67 mg, 0.09 mmol, 71%). Rf =0.67 (CH2Cl2/MeOH=95:5, v/v);
13C NMR (75 MHz, CDCl3, 258C, TMS): d=21.53, 103.15, 121.75, 127.55,
ꢁ131, 134.40, 137.73, 138.57 ppm; UV/Vis (CH2Cl2): lmax (lg e)=423
(5.03), 523 (4.21), 558 (4.07), 602 (3.77), 659 nm (3.81); MS (TOF, MS,
ES+, 70 eV): m/z (%): 646 (49, [M]+); HRMS: m/z: calcd for
[C34H24N4Br2]: 646.0368 [M]+; found: 646.0347.
m.p.>3008C; 1H NMR (300 MHz, CDCl3, 258C, TMS): d=ꢀ2.68 (brs,
2H, NH), 2.69 (s, 6H, Ar CH3), 3.22 (s, 12H, N
(CH3)2), 7.09 (AB, 3J=
ꢀ
3
3
3
J= J= J=8.8 Hz, 4H, 5,10-Ar Hm), 7.53 (AB, 3J=3J=3J=3J=7.7 Hz,
ꢀ
3
3
3
3
ꢀ
ꢀ
4H, 15,20-Ar Hm), 8.07 (AB, J= J= J= J=8.8 Hz, 4H, 5,10-Ar Ho),
3
3
3
3
ꢀ
8.09 (AB, J= J= J= J=7.7 Hz, 4H, 15,20-Ar Ho), 8.81 ppm (m, 8H,
Hb); 13C NMR (75 MHz, CDCl3, 258C, TMS): d=21.52, 40.74, 110.67,
119.46, 120.89, 127.35, 130.46, 134.51, 135.74, 137.15, 139.49, 149.90 ppm;
UV/Vis (CH2Cl2): lmax (lg e)=425 (4.86), 522 (4.13), 565 (4.15), 598 (sh),
656 nm (3.90); MS (TOF, MS, ES+, 70 eV): m/z (%): 728 (100, [M]+);
HRMS: m/z: calcd for [C50H44N6]: 728.3627 [M]+; found: 728.3624.
AHCTUNGTRENGN{UN (all-E)-5,10-Bis[4-(2-butoxycarbonylethenyl]-15,20-bis(4-methylphenyl)-
porphyrinato}zinc(II) (32): Compound 30 (77.7 mg, 0.11 mmol) was react-
ed with butyl acrylate (1.00 mL, 7.01 mmol) by following procedure E to
yield purple crystals (60 mg, 0.07 mmol, 64%). Rf =0.34 (CH2Cl2, 1%
triethylamine, v/v, alumina); m.p. 1768C; 1H NMR (500 MHz, CDCl3,
258C, TMS): d=1.08 (t, 3J=3J=7.4 Hz, 6H, C3H6CH3), 1.60 (m, 4H,
ꢀ
5,10-Bis(4-hydroxyphenyl)-15,20-bis(4-methylphenyl)porphyrin
(24):
C2H4CH2CH3), 1.88 (m, 4H, CH2CH2C2H5), 2.70 (s, 6H, Ar CH3), 4.43
Compound 12 (52 mg, 0.11 mmol) was reacted with 4-hydroxyphenyllithi-
um by following procedure B. Purification on silica gel (CH2Cl2) and re-
crystallization from CH2Cl2/MeOH gave purple crystals (41 mg,
0.06 mmol, 57%). Rf =0.36 (CH2Cl2); m.p. 1028C; 1H NMR (300 MHz,
(t, 3J=3J=6.8 Hz, 4H, CH2C3H7), 6.73 (d, 3J=3J=15.7 Hz, 2H, CH=
CH CO), 7.54 (d, J= J= J= J=7.5 Hz, 4H, Ar Hm), 7.99 (d, 3J=3J=
3
3
3
3
ꢀ
ꢀ
J= J=7.5 Hz, 4H, Ar Ho), 8.70 (s, 2H, Hb17,18), 8.84 (AB, 3J=3J=
3
3
ꢀ
4.7 Hz, 2H, Hb2,13), 9.39 (AB, 3J=3J=4.7 Hz, 2H, Hb3,12), 9.52 (s, 2H,
CDCl3, 258C, TMS): d=2.67 (s, 6H, Ar CH3), 7.01 (AB, 3J=3J=3J=
H
b7,8), 10.23 ppm (d, 3J=3J=15.7 Hz, 2H, CH=CH CO); 13C NMR
ꢀ
ꢀ
3J=8.2 Hz, 4H, 5,10-Ar Hm), 7.52 (AB, 3J=3J=3J=3J=7.6 Hz, 4H,
(126 MHz, CDCl3, 258C, TMS): d=13.74, 19.46, 21.26, 31.06, 64.66,
112.98, 123.51, 127.19, 128.77, 129.80, 130.09, 131.80, 132.78, 134.44,
137.21, 140.03, 146.86, 148.97, 149.41, 149.67, 150.31, 166.38 ppm; UV/Vis
(CH2Cl2): lmax (lg e)=438 (5.14), 572 (4.00), 616 nm (3.92); MS (TOF,
MS, ES+, 70 eV): m/z (%): 805 (100, [M+H]+); HRMS: m/z: calcd for
[C48H45N4O4Zn]: 805.2732 [M+H]+; found: 805.2706.
ꢀ
3
3
3
3
ꢀ
ꢀ
15,20-Ar Hm), 7.98 (AB, J= J= J= J=8.2 Hz, 4H, 5,10-Ar Ho), 8.07
3
3
3
3
ꢀ
(AB, J= J= J= J=7.6 Hz, 4H, 15,20-Ar Ho), 8.84 ppm (m, 8H, Hb);
UV/Vis (CH2Cl2): lmax (lg e)=420 (4.88), 517 (3.83), 553 (3.64), 592
(3.42), 648 nm (3.43); MS (TOF, MS, ES+, 70 eV): m/z (%): 674 (27,
[M]+), 337 (2, [M]2+); HRMS: m/z: calcd for [C46H34N4O2]: 674.2682
[M]+; found: 674.2645.
AHCTUNGTRENGN{UN (all-E)-5,10-Bis(4-methylphenyl)-15,20-bis[4-(3-oxobut-1-enyl]porphyri-
5,10-Bis(4-ethynylphenyl)-15,20-bis(4-methylphenyl)porphyrin (27): By
following procedure B, n-butyllithium (4 mL of 2.5m solution in n-
hexane, 10 mmol) was slowly added (ca. 1 h) under an argon atmosphere
to a 100 mL Schlenk flask charged with a solution of p-bromophenyl-
ethyne (0.91 g, 5.0 mmol) in of dry diethyl ether (15 mL) at ꢀ708C. The
reaction mixture was then warmed to ꢀ408C and THF was added drop-
wise until the aryllithium was formed as a white/pink suspension. A solu-
tion of compound 12 (56 mg, 0.125 mmol) in of dry THF (50 mL) was
added rapidly. The color of the mixture changed from deep purple to
brown within 30 min, subsequently a mixture of water (5 mL) in of THF
(5 mL) was added for hydrolysis. After stirring of the mixture for 20 min,
a solution of DDQ (283 mg, 1.25 mmol) in CH2Cl2 was added and the re-
action mixture was stirred for another 60 min at RT. The crude product
was subjected to column chromatography with CH2Cl2/n-hexane (1:1,
v/v) to give 24 mg (0.034 mmol, 31%), of a purple solid after recrystalli-
zation from CH2Cl2/MeOH. Rf =0.73 (CH2Cl2/n-hexane=1:1, v/v); m.p.>
nato}zinc(II) (33): Compound 30 (77.7 mg, 0.11 mmol) was reacted with
methyl vinyl ketone (0.57 mL, 7.02 mmol) by following procedure E to
yield purple crystals (35 mg, 0.05 mmol, 50%). Rf =0.5 (CH2Cl2, 5%
MeOH, v/v); m.p. 2158C; 1H NMR (300 MHz, CDCl3, 258C, TMS): d=
2.50 (s, 6H, CO CH3), 2.71 (s, 6H, Ar CH3), 6.58 (d, 3J=3J=15.7 Hz,
ꢀ
ꢀ
3
3
3
3
ꢀ
ꢀ
2H, CH=CH CO), 7.55 (AB, J= J= J= J=7.5 Hz, 4H, Ar Hm), 8.00
3
3
3
3
ꢀ
(d, J= J= J= J=7.5 Hz, 4H, Ar Ho), 8.80 (s, 2H, Hb17,18), 8.89 (AB,
3J=3J=4.7 Hz, 2H, Hb2,13), 9.22 (s, 2H, Hb7,8), 9.28 (AB, 3J=3J=4.7 Hz,
2H, Hb3,12), 9.80 ppm (d, J= J=15.7 Hz, 2H, CH=CH CO); 13C NMR
(63 MHz, CDCl3, 258C, TMS): d=20.78, 27.29, 112.81, 123.21, 126.81,
128.53, 129.33, 131.04, 131.61, 132.49, 133.88, 136.96, 139.20, 144.93,
148.25, 148.83, 149.32, 149.98, 196.33 ppm; UV/Vis (CH2Cl2): lmax (lg e)=
443 (4.44), 577 (4.18), 621 nm (4.14); MS (TOF, MS, ES+, 70 eV): m/z
(%): 689 (100, [M+H]+); HRMS: m/z: calcd for [C42H33N4O2Zn]:
689.1895 [M]+; found: 689.1889.
3
3
ꢀ
AHCTUNGTRENGN{UN (all-E)-5,10-Bis(4-methylphenyl)-15,20-bis[2-(3-nitro-phenyl)vinyl]por-
3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.78 (s, 2H, NH),
phyrinato}zinc(II) (34): By following the general procedure E, compound
30 (100 mg, 0.140 mmol), was dissolved in DMF (50 mL) under a nitro-
gen atmosphere. 3-Nitrostyrene (1.36 mL, 9.8 mmol), sodium acetate
(65 mg, 0.784 mmol), palladium acetate (3.1 mg, 0.014 mmol), and triphe-
nylphosphine (14.7 mg, 0.056 mmol) were added and the temperature
was raised to 1208C for 16 h (TLC control). The crude product was ex-
tracted with CH2Cl2 and washed with water. The product was purified by
silica-gel column chromatography with CH2Cl2/n-hexane (1:1, v/v) and
gave 70 mg (0.082 mmol, 60%) of the desired compound after recrystalli-
zation from CH2Cl2/MeOH. Rf =0.12 (CH2Cl2/n-hexane=1:1, v/v); m.p.>
3
ꢀ
ꢀ ꢂ
ꢀ
2.73 (s, 6H, Ar CH3), 3.34 (s, 2H, C CH), 7.58 (d, J=7.6 Hz, 4H, Ar
3
3
ꢀ
ꢀ
H), 7.92 (d, J=8.2 Hz, 4H, Ar H), 8.11 (d, J=7.6 Hz, 4H, Ar H), 8.20
(d, J=7.6 Hz, 4H, Ar H), 8.84 (m, 4H, Hb), 8.90 ppm (m, 4H, Hb);
3
ꢀ
13C NMR (63 MHz, CDCl3, 258C, TMS): d=21.09, 77.84, 83.22, 118.42,
120.29, 121.14, 127.01, 130.17, 134.06, 134.19, 137.03, 138.61, 142.37 ppm;
UV/Vis (DMF): lmax (lg e)=420 (4.92), 516 (3.61), 551 (3.38), 592 (3.20),
655 nm (3.19); HRMS: m/z: calcd for [C50H35N4]: 691.2862 [M+H]+;
found: 691.2858.
5,10-Bis(4-ethynylphenyl)-15,20-bis(2,6-difluorophenyl)porphyrin
(28):
By following procedure B and the details given for 27, reaction of p-bro-
mophenylethyne (0.55 g, 3.0 mmol) and compound 16 (40 mg,
0.075 mmol) gave 14 mg (0.019 mmol, 25%) of the title compound. Rf =
0.6 (CH2Cl2/n-hexane=1:1, v/v); m.p.>3008C; 1H NMR (400 MHz,
3008C; 1H NMR (600 MHz, CD2Cl2, 258C, TMS): d=2.76 (s, 6H, CH3),
3
6.58 (d, 3J=16 Hz, 2H, vinyl), 7.49 (d, J=7.7 Hz, 4H, Ar H), 7.69 (t,
ꢀ
J=7.7 Hz, 4H, Ar H), 7.91 (d, J=7.7 Hz, 4H, Ar H), 7.93 (d, 3J=
3
3
ꢀ
ꢀ
3
ꢀ
ꢀ
7.7 Hz, 2H, Ar H), 8.29 (d, J=8.2 Hz, 2H, Ar H), 8.65 (s, 2H, Hb),
8.71 (d, 3J=16 Hz, 2H, vinyl), 8.88 (s, 2H, Hb), 8.93 (d, 3J=4.4 Hz, 2H,
Hb), 9.23 ppm (d, 3J=4.4 Hz, 2H, Hb); 13C NMR (125 MHz, CD2Cl2,
258C, TMS): d=138.67, 139.29, 146.90, 148.53, 148.92, 149.72,
150.38 ppm; UV/Vis (DMF): lmax (lg e)=445 (5.12), 584 (3.98), 630 nm
(3.80).
ꢀ ꢂ
CDCl3, 258C, TMS): d=ꢀ2.71 (s, 2H, NH), 3.51 (s, 2H, C CH), 7.43
3
(t, J=8.2 Hz, 4H, Ar H), 7.81 (m, 2H, Ar H), 7.96 (t, 3J=8.2 Hz, 4H,
ꢀ
ꢀ
3
ꢀ
ꢀ
Ar H), 8.23 (t, J=7.6 Hz, 4H, Ar H), 8.92 (m, 4H, Hb), 9.02 ppm (m,
4H, Hb); UV/Vis (DMF): lmax (lg e)=414 (5.09), 508 (3.83), 543 (3.18),
585 (3.30), 637 nm (2.89); HRMS: m/z: calcd for [C48H27F4N4]: 735.2172
[M+H]+; found: 735.2197.
AHCTUNGTRENGN{UN (all-E)-5,10-Bis(4-methylphenyl)-15,20-[2-(3-nitrophenyl)vinyl] porphyri-
5,10-Dibromo-15,20-bis(4-methylphenyl)porphyrin (29): Compound 12
(93 mg, 0.19 mmol) was reacted with NBS (84 mg, 0.47 mmol) by follow-
ing procedure C to yield purple crystals (102 mg, 0.16 mmol, 83%). Rf =
nato}nickel(II) (35): By following the general procedure E, compound 31
(25 mg, 0.140 mmol), 3-nitrostyrene (0.35 mL, 2.48 mmol), sodium acetate
(16 mg, 0.196 mmol), palladium acetate (0.8 mg, 0.003 mmol), and triphe-
nylphosphine (3.7 mg, 0.014 mmol) in DMF (50 mL) gave 5 mg
(0.006 mmol, 34%) of a purple compound after recrystallization from
CH2Cl2/MeOH. Rf =0.47 (CH2Cl2/n-hexane=1:1, v/v); m.p.>3008C;
1H NMR (400 MHz, CDCl3, 258C, TMS): d=2.66 (s, 6H, CH3), 6.71 (d,
1
0.59 (CH2Cl2/n-hexane=1:1, v/v); m.p. 2858C (dec); H NMR (300 MHz,
ꢀ
CDCl3, 258C, TMS): d=ꢀ2.91 (brs, 2H, NH), 2.69 (s, 6H, Ar CH3),
3
3
3
3
7.54 (AB, J= J= J= J=7.9 Hz, 4H, Ar Hm), 8.01 (AB, 3J=3J=3J=
ꢀ
J=7.9 Hz, 4H, Ar Ho), 8.74 (s, 2H, Hb17,18), 8.82 (AB, 3J=3J=4.8 Hz,
3
ꢀ
2H, Hb2,13), 9.52 (AB, J=3J=4.8 Hz, 2H, Hb3,12), 9.54 ppm (s, 2H, Hb7,8);
J=15.8 Hz, 2H, alkene H), 7.49 (d, J=7.6 Hz, 4H, Ar H), 7.64 (t, J=
3
3
3
3
ꢀ
ꢀ
Chem. Eur. J. 2011, 17, 13562 – 13573
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
13569

M. O. Senge et al.
3
7.6 Hz, 2H, Ar H), 7.82 (d, J=7.6 Hz, 4H, Ar H), 7.93 (d, 3J=7.7 Hz,
5,10-Bis(4-methylphenyl)-15,20-bis(4-nitrophenyl)porphyrin (45): By fol-
lowing the general procedure F, compound 29 (30 mg, 0.0462 mmol), 4-ni-
trophenylboronic acid pinacol ester (116 mg, 0.462 mmol), [PdACHTUNGTRENNUNG(PPh3)4]
ꢀ
ꢀ
3
ꢀ
ꢀ
ꢀ
2H, Ar H), 8.22 (d, J=7.6 Hz, 2H, Ar H), 8.59 (s, 2H, Ar H), 8.61 (s,
2H, Hb), 8.73 (d, 3J=4.7 Hz, 2H, Hb), 9.14 (d, 3J=4.7 Hz, 2H, Hb), 9.18
(d, 3J=15.8 Hz, 2H, alkene H), 9.23 ppm (s, 2H, Hb); 13C NMR
ꢀ
(5.3 mg, 0.0046 mmol), and K3PO4 (196 mg, 0.925 mmol) in THF (50 mL)
gave 16 mg (0.021 mmol, 47%) of a purple solid after recrystallization
from CH2Cl2/MeOH. Rf =0.5 (CH2Cl2/n-hexane=1:1, v/v); m.p.>
(150 MHz, CD2Cl2, 258C, TMS): d=21.44, 29.34, 112.65, 120.79, 122.47,
127.78, 129.56, 129.84, 130.91, 132.22, 133.38, 137.61, 138.51, 139.87,
141.39, 142.31, 148.63 ppm; UV/Vis (DMF): lmax (lg e)=444 (4.87), 563
(3.83), 614 nm (3.75).
3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.76 (s, 2H, NH),
3
2.74 (s, 6H, CH3), 7.60 (d, J=7.6 Hz, 4H, Ar H), 8.11 (d, 3J=7.6 Hz,
ꢀ
4H, Ar H), 8.42 (d, J=8.2 Hz, 4H, Ar H), 8.67 (d, 3J=8.2 Hz, 4H,
3
ꢀ
ꢀ
5,10-Dibromo-15,20-di(n-pentylporphyrin (39): By following the general
procedure C 5,10-diACHTUNGTRENNUNG(n-pentyl)porphyrin (90 mg, 0.2 mmol) and NBS
Ar H), 8.76 (d, 3J=4.7 Hz, 2H, Hb), 8.80 (s, 2H, Hb), 8.92 (s, 2H, Hb),
ꢀ
8.96 ppm (d, 3J=4.7 Hz, 2H, Hb); 13C NMR (125 MHz, CDCl3, 258C,
TMS): d=21.09, 116.47, 121.48, 127.12, 134.66, 137.33, 138.25, 147.31,
148.53 ppm; UV/Vis (DMF): lmax (lg e)=421 (4.90), 516 (3.64), 552
(3.46), 584 (3.34), 655 nm (3.60); HRMS (MS ES+): m/z: calcd for
[C46H32N6O4]: 733.2563 [M+H]+; found 733.2573.
(89 mg, 0.5 mmol) gave 73 mg (0.12 mmol, 60%) of a purple solid after
recrystallization from CH2Cl2/MeOH. Rf =0.62 (CH2Cl2/n-hexane=2:1,
v/v); m.p.>1988C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ3.15
3
(s, 2H, NH), 1.00 (t, J=7.3, 7.0 Hz, 6H, CH2CH2CH2CH2CH3), 1.56 (m,
4H, CH2CH2CH2CH2CH3), 1.77 (m, 4H, CH2CH2CH2CH2CH3), 2.44 (m,
4H,
CH2CH2CH2CH2CH3),
4.77
(t,
3J=7.7,
8 Hz,
4H,
5,10-Bis(4-methylphenyl)-15,20-bis(3-nitrophenyl)porphyrin (46): By fol-
lowing the general procedure F, compound 29 (33 mg, 0.05 mmol), 4-
methoxycarbonylphenyl boronic acid (90 mg, 0.5 mmol), [PdACHTUNGTRENNUNG(PPh3)4]
CH2CH2CH2CH2CH3), 9.20 (m, 4H, Hb), 9.49 ppm (m, 4H, Hb);
13C NMR (150 MHz, 258C, CDCl3): d=13.86, 22.71, 29.40, 32.40, 35.24,
38.25, 101.90, 121.45 ppm; UV/Vis (DMF): lmax (lg e)=422 (4.48), 524
(3.48), 559 (3.25), 605 (2.78), 664 nm (3.14); HRMS (ES+): m/z: calcd
for [C30H33N4Br2]: 607.1072 [M+H]+; found: 607.1097.
(5.8 mg, 0.005 mmol), and K3PO4 (212 mg, 1 mmol) in THF (60 mL) gave
10 mg (0.013 mmol, 30%) of a purple solid after recrystallization from
CH2Cl2/MeOH. Rf =0.3 (CH2Cl2/n-hexane=1:1, v/v); m.p.>3008C;
1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.77 (s, 2H, NH), 2.74 (s,
5,10-Bis(4-bromophenyl)porphyrin (41): 4-Bromobenzaldehyde (0.74 g,
4 mmol) was reacted according to
3
3
ꢀ
ꢀ
6H, CH3), 7.60 (d, J=7.6 Hz, 4H, Ar H), 7.99 (t, J=7.6 Hz, 2H, Ar
a
procedure described before.[12]
H), 8.13 (d, J=7 Hz, 2H, Ar H), 8.57 (m, 2H, Ar H), 8.72 (d, 3J=
3
ꢀ
ꢀ
Column chromatography on silica gel (CH2Cl2/n-hexane=1:4, v/v) gave
compound 71 as the first fraction, followed by the title compound and
then traces of (4-bromophenyl)porphyrin. Recrystallization from CH2Cl2/
MeOH gave 46 mg (0.07 mmol, 4%) as purple crystals. Rf =0.38 (CH2Cl2/
n-hexane=1:1, v/v); m.p.>3008C; 1H NMR (500 MHz, CDCl3, 258C,
TMS): d=ꢀ3.45 (brs, 2H, NH), 7.89 (AB, 3J=3J=3J=3J=8.1 Hz, 4H,
8.2 Hz, 4H, Ar H), 8.79 (d, 3J=4.7 Hz, 2H, Hb), 8.93 (s, 2H, Hb), 8.96
ꢀ
(d, 3J=4.7 Hz, 2H, Hb), 9.11 ppm (s, 2H, Hb); 13C NMR (125 MHz,
CDCl3, 258C, TMS): d=29.59, 116.46, 121.52, 122.88, 127.44, 127.66,
128.20, 134.38, 137.61, 138.62, 139.69, 143.64, 146.84 ppm; UV/Vis
(DMF): lmax (lg e)=421 (4.90), 516 (3.64), 551 (3.46), 589 (3.34), 646 nm
(3.16); HRMS (MS ES+): m/z: calcd for [C44H32N4O4]: 733.2563 [M+H]+
; found 733.2540.
3
3
3
3
ꢀ
ꢀ
Ar Hm), 8.05 (AB, J= J= J= J= =8.1 Hz, 4H, Ar Ho), 8.89 (s, 2H,
H
b7,8), 8.96 (AB, 3J=3J=4.7 Hz, 2H, Hb2,13), 9.30 (AB, 3J=3J=4.7 Hz,
5,10-Bis(3-cyanophenyl)-15,20-bis(4-methylphenyl)porphyrin (47): By fol-
lowing the general procedure F, compound 29 (20 mg, 0.0308 mmol), 4-
cyanophenyl boronic acid (46 mg, 0.308 mmol), [PdACTHUNTRGNE(UNG PPh3)4] (3.6 mg,
2H, Hb3,12), 9.38 (s, 2H, Hb17,18), 10.17 ppm (s, 2H, Hmeso); 13C NMR
(63 MHz, CDCl3, 258C, TMS): d=104.53, 118.41, 122.52, 129.90, ~131,
135.89, 140.98 ppm; UV/Vis (CH2Cl2): lmax (lg e)=407 (5.36), 502 (4.33),
0.003 mmol), and K3PO4 (131 mg, 0.617 mmol) in THF (60 mL) gave
534 (3.67), 575 (3.87), 629 nm (3.38); MS (70 eV, EI): m/z (%): 620 (9,
1
10 mg (0.014 mmol, 47%) of the desired product. M.p.>3008C; H NMR
[M]·+), 540 (4, [MꢀBr] ), 464 (3, [MꢀC6H4Br+Br] +), 310 (14, [M]2+);
+
C
ꢀ
(400 MHz, CDCl3, 258C, TMS): d=ꢀ2.79 (s, 2H, NH), 2.74 (s, 6H,
HRMS: m/z: calcd for [C32H20N4Br2]: 618.0055 [M]+; found: 618.0061.
3
ꢀ
ꢀ
CH3), 7.61 (d, J=7 Hz, 4H, Ar H), 7.92 (m, 2H, Ar H), 8.14 (m, 6H,
3
5,10-Bis(4-methoxycarbonylphenyl)-15,20-bis(4-methylphenyl)porphyrin
(43): By following the general procedure F, compound 29 (33 mg,
0.05 mmol), 4-methoxycarbonylphenyl boronic acid (90 mg, 0.5 mmol),
[PdACHTUNGTRENNUNG(PPh3)4] (5.8 mg, 0.005 mmol), and K3PO4 (212 mg, 1 mmol) in THF
(60 mL) gave 20 mg (0.02 mmol, 52%) of a purple solid after recrystalli-
ꢀ
ꢀ
Ar H), 8.49 (t, J=7, 6.4 Hz, 2H, Ar H), 8.55 (m, 2H, Ar-H), 8.74 (d,
3J=4.7 Hz, 2H, Hb), 8.78 (s, 2H, Hb), 8.93 (s, 2H, Hb), 8.96 ppm (d, 3J=
4.7 Hz, 2H, Hb); 13C NMR (150 MHz, CDCl3, 258C, TMS): d=21.10,
110.92, 116.32, 118.48, 121.10, 127.25, 131.16, 134.10, 136.62, 137.26,
137.84, 138.32, 142.99 ppm; UV/Vis (DMF): lmax (log e)=419 (4.88), 514
(3.61), 548 (3.44), 589 (3.31), 646 nm (3.38); HRMS (MS ES+): m/z:
calcd for [C48H32N6]: 693.2767 [M+H]+; found 693.2743.
zation from CH2Cl2/MeOH. Rf =0.28 (CH2Cl2/n-hexane=1:1, v/v); m.p.>
3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.76 (s, 2H, NH),
3
ꢀ
2.70 (s, 6H, CH3), 4.13 (s, 6H, OCH3), 7.59 (d, J=7.6 Hz, 4H, Ar H),
5,10-Bis(4-methoxycarbonylphenyl)-15,20-diphenylporphyrin (48): By fol-
lowing the general procedure F, compound 36 (30 mg, 0.048 mmol), 4-
methoxycarbonylphenylboronic acid (86 mg, 0.48 mmol), [PdACHTUNGTRENNUNG(PPh3)4]
3
3
ꢀ
ꢀ
8.12 (d, J=7.6 Hz, 4H, Ar H), 8.32 (d, J=8.2 Hz, 4H, Ar H), 8.46 (d,
J=8.2 Hz, 4H, Ar H), 8.80 (d, 3J=4.7 Hz, 2H, Hb), 8.82 (s, 2H, Hb),
3
ꢀ
8.90 (s, 2H, Hb), 8.92 ppm (d, 3J=4.7 Hz, 2H, Hb); 13C NMR (125 MHz,
CDCl3, 258C, TMS): d=21.46, 52.37, 118.09, 120.85, 126.80, 127.03,
127.48, 129.12, 129.76, 134.10, 137.09, 138.54, 146.66, 166.89 ppm; UV/Vis
(DMF): lmax (lg e)=420 (4.92), 516 (4.27), 551 (4.08), 581 (3.87), 655 nm
(3.97); HRMS (MS ES+): m/z: calcd for [C50H39N4O4]: 759.2971 [M+H]+
; found 759.2941.
(5.5 mg, 0.005 mmol), and K3PO4 (205 mg, 0.967 mmol) in THF (50 mL)
gave 10 mg (0.013 mmol, 30%) of a purple solid after recrystallization
from CH2Cl2/MeOH. Rf =0.5 (CH2Cl2/n-hexane=1:1, v/v); m.p.>
3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.76 (s, 2H, NH),
3
4.14 (s, 6H, CH3), 7.79 (d, J=7.6 Hz, 4H, Ar H), 8.24 (d, 3J=8.2 Hz,
ꢀ
4H, Ar H), 8.33 (d, J=8.2 Hz, 4H, Ar H), 8.47 (d, 3J=8.2 Hz, 4H,
3
ꢀ
ꢀ
Ar H), 8.82 (m, 4H, Hb), 8.90 ppm (m, 4H, Hb); 13C NMR (125 MHz,
ꢀ
5,10-Bis(4-cyanophenyl)-15,20-bis(4-methylphenyl)porphyrin (44): By fol-
lowing the general procedure F, compound 29 (30 mg, 0.046 mmol), 4-cy-
anophenyl boronic acid (68 mg, 0.46 mmol), [PdACHTNUTRGNE(UNG PPh3)4] (5.3 mg,
CDCl3, 258C, TMS): d=45.57, 51.99, 118.30, 126.29, 127.44, 129.19,
134.07, 141.47, 146.45, 166.85 ppm; UV/Vis (DMF): lmax (lg e)=418
(4.94), 514 (3.80), 548ACTHNUTRGNE(NUG 3.61), 588 (3.34), 646 nm (3.32); HRMS (MS
0.0046 mmol), and K3PO4 (196 mg, 0.925 mmol) in THF (50 mL) gave
15 mg (0.021 mmol, 47%) of a purple solid after recrystallization from
CH2Cl2/MeOH. Rf =0.34 (CH2Cl2/n-hexane=1:1, v/v); m.p.>3008C;
ES+): m/z: cacld for [C48H35N4O4]: 731.2658 [M+H]+, found 731.2625.
5,10-Bis(4-cyanophenyl)-15,20-diphenylporphyrin (49): By following the
general procedure F, compound 36 (20 mg, 0.032 mmol), 4-cyanophenyl-
boronic acid (47 mg, 0.32 mol), [PdACHTNUGTRNEUNG(PPh3)4] (3.7 mg, 0.003 mmol), and
K3PO4 (136 mg, 0.644 mmol) in THF (50 mL) gave 6 mg (0.009 mmol,
29%) of a purple solid after recrystallization from CH2Cl2/MeOH. Rf =
0.3 (CH2Cl2/n-hexane=1:1, v/v); m.p.>3008C; 1H NMR (400 MHz,
1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.79 (s, 2H, NH), 2.74 (s,
3
ꢀ
ꢀ
6H, CH3), 7.60 (d, J=8.2 Hz, 4H, Ar H), 8.10 (m, 8H, Ar H), 8.36 (d,
J=8.2 Hz, 4H, Ar H), 8.75 (d, 3J=4.7 Hz, 2H, Hb), 8.78 (s, 2H, Hb),
3
ꢀ
8.92 (s, 2H, Hb), 8.95 ppm (d, 3J=4.7 Hz, 2H, Hb); 13C NMR (125 MHz,
CDCl3, 258C, TMS): d=21.10, 111.51, 118.57, 121.13, 130.13, 134.29,
137.11, 137.28, 138.30, 146.55 , ppm; UV/Vis (DMF): lmax (lg e)=420
(4.94), 515 (3.79), 551 (3.62), 584 (3.44), 655 nm (3.68); HRMS (MS
ES+): m/z: calcd for [C48H33N6]: 693.2767 [M+H]+, found 693.2734.
ꢀ
CDCl3, 258C, TMS): d=ꢀ2.80 (s, 2H, NH), 7.80 (m, 4H, Ar H), 8.11 (d,
3
3
J=7.6 Hz, 4H, Ar H), 8.23 (d, J=7.6 Hz, 4H, Ar H), 8.37 (d, 3J=
ꢀ
ꢀ
3
ꢀ
8.2 Hz, 4H, Ar H), 8.76 (d, J=4.7 Hz, 2H, Hb), 8.80 (s, 2H, Hb), 8.90 (s,
13570
www.chemeurj.org
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 13562 – 13573

Porphyrins with Realigned Dipole Moment
FULL PAPER
2H, Hb), 8.93 ppm (d, 2H, 3J=4.7 Hz, Hb); 13C NMR (150 MHz, CDCl3,
258C, TMS): d=29.26, 111.58, 117.12, 118.54, 120.94, 126.37, 127.56,
130.14, 130.23, 134.08, 134.52, 141.22, 146.48 ppm; UV/Vis (DMF): lmax
(lg e)=418 (4.98), 514 (3.64), 548 (3.26), 588 (2.87), 645 nm (2.56);
HRMS (MS ES+): m/z: calcd for [C46H29N6]: 665.2454 [M+H]+; found
665.2468.
THF (30 mL) gave 7 mg (0.008 mmol, 30%) of purple solid after recrys-
tallization from CH2Cl2/MeOH. Rf =0.5 (CH2Cl2/n-hexane=1:1, v/v);
1
m.p.>3008C; H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.72 (s, 2H,
3
ꢀ
NH), 4.15 (s, 6H, CH3), 7.42 (t, J=6.4 Hz, 4H, Ar H), 7.83 (m, 2H,
3
3
ꢀ
ꢀ
ꢀ
Ar H), 8.34 (d, J=8.2 Hz, 4H, Ar H), 8.38 (d, J=8.2 Hz, 4H, Ar H),
8.93 ppm (m, 8H, Hb); UV/Vis (CH2Cl2): lmax (lg e)=416 (4.98), 511
(3.77), 547 (3.30), 590 (3.27), 647 nm (2.95); HRMS (MS ES+): m/z:
calcd for [C48H31N4O4F4]: 803.2281 [M+H]+; found 803.2261.
5,10-Bis(4-nitrophenyl)-15,20-diphenylporphyrin (50): By following the
general procedure F, compound 36 (20 mg, 0.032 mmol), 4-nitrophenyl
boronic pinacol ester (80 mg, 0.32 mmol), [PdACTHNUTRGNE(UNG PPh3)4] (3.7 mg,
5,10-Bis(4-cyanophenyl)-15,20-bis(2,6-difluorophenyl)porphyrin (55): By
following the general procedure F, compound 38 (20 mg, 0.028 mmol), 4-
cyanophenylboronic acid (52 mg, 0.35 mol), [PdACHTNUTRGNE(UNG PPh3)4] (3.2 mg,
0.003 mmol), and K3PO4 (135 mg, 0.64 mmol) in THF (60 mL) gave
10 mg (0.014 mmol, 43%) of the title compound. Rf =0.3 (CH2Cl2/n-
hexane=1:1, v/v); m.p.>3008C; 1H NMR (400 MHz, CDCl3, 258C,
0.003 mmol), and K3PO4 (154 mg, 0.722 mmol) in THF (30 mL) gave
6 mg (0.008 mmol, 28%) of purple solid after recrystallization from
CH2Cl2/MeOH. Rf =0.5 (CH2Cl2/n-hexane=1:1, v/v); m.p.> 3008C;
TMS): d=ꢀ2.77 (s, 2H, NH), 7.82 (m, 4H, Ar H), 8.23 (d, 3J=6.4 Hz,
ꢀ
3
4H, Ar H), 8.42 (d, J=8.8 Hz, 4H, Ar H), 8.67 (d, 3J=8.8 Hz, 4H,
ꢀ
ꢀ
Ar H), 8.78 (d, 3J=4.7 Hz, 2H, Hb), 8.82 (s, 2H, Hb), 8.90 (s, 2H, Hb),
8.94 ppm (d, J=4.7 Hz, 2H, Hb); UV/Vis (DMF): lmax (lg e)=421 (4.95),
ꢀ
1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.78 (s, 2H, NH), 7.42 (t,
3
3
J=8.7, 7.6 Hz, 4H, Ar H), 7.85 (m, 2H, Ar H), 8.10 (d, 3J=8.2 Hz,
ꢀ
ꢀ
3
516 (3.69), 552 (3.58), 592 (3.29), 646 nm (3.45); HRMS (MS ES+) m/z:
calcd for [C44H29N6O4]: 705.2250 [M+H]+; found 705.2278.
ꢀ
ꢀ
4H, Ar H), 8.35 (d, J=8.2 Hz, 4H, Ar H), 8.78 (s, 2H, Hb), 8.81 (d,
3J=4.7 Hz, 2H, Hb), 8.91 (d, 3J=4.7 Hz, 2H, Hb), 8.93 ppm (s, 2H, Hb);
UV/Vis (CH2Cl2): lmax (lg e)=417 (5.06), 511 (3.81), 548 (3.26), 585
(3.31), 645 nm (2.96); HRMS (MS ES+): m/z: calcd for [C46H25N6F4]:
737.2077 [M+H]+; found 737.2088.
5,10-Bis(4-methoxycarbonylphenyl)-15,20-bis(3-methoxyphenyl)porphy-
rin (51): By following the general procedure F, compound 37 (20 mg,
0.029 mmol), 4-methoxycarbonylphenylboronic acid (52 mg, 0.293 mmol),
[PdACHTUNGTRENNUNG(PPh3)4] (3.3 mg, 0.0029 mmol), and K3PO4 (124 mg, 0.587 mmol) in
THF (50 mL) gave 9 mg (0.011 mmol, 32%) of a purple solid after re-
5,10-Bis(2,6-difluorophenyl)-15,20-bis(4-nitrophenyl)porphyrin (56): By
following the general procedure F, compound 38 (20 mg, 0.028 mmol), 4-
nitrophenyl boronic pinacol ester (91 mg, 0.364 mmol), [PdACHTUNGTRENNUNG(PPh3)4]
crystallization from CH2Cl2/MeOH. Rf =0.3 (CH2Cl2/n-hexane=1:1, v/v);
1
m.p.>3008C; H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.78 (s, 2H,
(3.2 mg, 0.003 mmol), and K3PO4 (154 mg, 0.722 mmol) in THF (30 mL)
NH), 4.01 (s, 6H, OCH3), 4.14 (s, 6H, OCH3), 7.37 (d, 3J=8.2 Hz, 2H,
gave 5 mg (0.006 mmol, 22%) of the title compound. Rf =0.5 (CH2Cl2/n-
3
3
ꢀ
ꢀ
ꢀ
Ar H), 7.67 (t, J=8.2 Hz, 2H, Ar H), 7.82 (d, J=7.6 Hz, 4H, Ar H),
hexane=1:1, v/v); m.p.>3008C; 1H NMR (400 MHz, CDCl3, 258C,
8.33 (d, 3J=7.6 Hz, 4H, Ar H), 8.47 (d, 3J=7.6 Hz, 4H, Ar H),
8.82 ppm (m, 4H, Hb), 8.93 (m, 4H, Hb); 13C NMR (125 MHz, CDCl3,
258C, TMS): d=52.33, 55.37, 113.46, 118.79, 120.35, 127.81, 129.48,
134.40, 143.06, 146.74, 157.80, 167.18 ppm; UV/Vis (DMF): lmax (lg e)=
419 (4.96), 514 (3.74), 549 (3.47), 588 (3.34), 646 nm (3.36); HRMS (MS
ES+): m/z: calcd for [C50H39N4O6]: 791.2870 [M+H]+; found 791.2865.
ꢀ
ꢀ
3
ꢀ
TMS): d=ꢀ2.75 (s, 2H, NH), 7.44 (t, J=8.2 Hz, 4H, Ar H), 7.85 (m,
2H, Ar H), 8.42 (d, J=8.7 Hz, 4H, Ar H), 8.68 (d, 3J=8.2 Hz, 4H,
3
ꢀ
ꢀ
3
3
ꢀ
Ar H), 8.81 (s, 2H, Hb), 8.83 (d, J=4.7 Hz, 2H, Hb), 8.92 (d, J=4.7 Hz,
2H, Hb), 8.94 ppm (s, 2H, Hb); UV/Vis (CH2Cl2): lmax (lg e)=418 (5.11),
512 (3.96), 550 (3.32), 591 (3.39), 646 nm (2.43); HRMS (MS ES+): m/z:
calcd for [C44H25N6O4F4]: 777.1873 [M+H]+; found 777.1884.
5,10-Bis(4-cyanophenyl)-15,20-bis(3-methoxyphenyl)porphyrin (52): By
following the general procedure F, compound 37 (30 mg, 0.044 mmol), 4-
cyanophenyl boronic acid (64 mg, 0.44 mmol), [PdACTHNUTRGNE(UNG PPh3)4] (5 mg,
5,10-Bis(4-methoxycarbonylphenyl)-15,20-di
following the general procedure F, compound 39 (30 mg, 0.049 mmol), 4-
methoxycarbonylphenylboronic acid (88 mg, 0.49 mmol), [Pd(PPh3)4]
ACHTUNGTNER(NUNG n-pentyl)porphyrin (57): By
ACHTUNGTRENNUNG
0.004 mmol), and K3PO4 (186 mg, 0.88 mmol) in THF (60 mL) gave
15 mg (0.020 mmol, 47%) of a purple solid after recrystallization from
CH2Cl2/MeOH. Rf =0.3 (CH2Cl2/n-hexane=1:1, v/v); m.p.>3008C;
(5.7 mg, 0.005 mmol), and K3PO4 (209 mg, 0.986 mmol) in THF (50 mL)
gave 20 mg (0.026 mmol, 57%) of the title compound. Rf =0.35 (CH2Cl2/
n-hexane=1:1, v/v); m.p.>3008C; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d=ꢀ2.68 (s, 2H, NH), 1.02 (t, 3J=7.6, 7.0 Hz, 6H,
CH2CH2CH2CH2CH3), 1.68 (m, 4H, CH2CH2CH2CH2CH3), 1.85 (m, 4H,
CH2CH2CH2CH2CH3), 2.58 (m, 4H, CH2CH2CH2CH2CH3), 4.14 (s, 6H,
1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.82 (s, 2H, NH), 4.02 (s,
3
ꢀ
ꢀ
6H, OCH3), 7.38 (m, 2H, Ar H), 7.69 (t, J=8.2 Hz, 4H, Ar H), 7.81
3
3
ꢀ
ꢀ
(m, 4H, Ar H), 8.10 (d, J=8.2 Hz, 4H, Ar H), 8.36 (d, J=7.6 Hz, 4H,
Ar H), 8.77 (d, 3J=4.7 Hz, 2H, Hb), 8.79 (s, 2H, Hb), 8.94 (s, 2H, Hb),
ꢀ
OCH3), 5.03 (t, 3J=8.2 Hz, 4H, CH2CH2CH2CH2CH3), 8.28 (d, 3J=
8.97 ppm (d, 3J=4.68 Hz, 2H, Hb); 13C NMR (125 MHz, CDCl3,
258C,TMS): d=55.07, 111.58, 113.19, 115.85, 117.18, 118.53, 120.56,
127.19, 130.14, 134.51, 142.51, 146.47, 157.55 ppm; UV/Vis (DMF): lmax
(lg e)=419 (4.90), 513 (3.56), 547 (3.25), 592 (3.16), 643 nm (3.18);
HRMS (MS ES+): m/z: calcd for [C48H33N6O2]: 725.2655 [M+H]+; found
725.2641.
3
ꢀ
ꢀ
8.2 Hz, 4H, Ar H), 8.45 (d, J=8.2 Hz, 4H, Ar H), 8.71 (s, 2H, Hb),
8.83 (d, 3J=4.7 Hz, 2H, Hb), 9.49 (d, 3J=4.7 Hz, 2H, Hb), 9.61 ppm (s,
2H, Hb); 13C NMR (150 MHz, CDCl3, 258C, TMS): d=13.35, 29.63,
32.33, 35.25, 38.21, 51.80, 116.90, 120.40, 126.79, 127.69, 129.01, 129.75,
134.04, 146.67, 166.92 ppm; UV/Vis (DMF): lmax (lg e)=418 (4.93), 518
(4.03), 550 (3.95), 592 (3.85), 651 nm (3.88); HRMS (MS ES+): m/z:
calcd for [C46H47N4O4]: 719.3597 [M+H]+; found 719.3620.
5,10-Bis(3-methoxyphenyl)-15,20-bis(4-nitrophenyl)porphyrin (53): By
following the general procedure F, compound 37 (20 mg, 0.03 mmol), 4-
5,10-Bis(4-cyanophenyl)-15,20-di
the general procedure F, compound 39 (40 mg, 0.065 mmol), 4-cyano-
phenyl boronic acid (95.5 mg, 0.65 mmol), [Pd(PPh3)4] (7.5 mg,
0.007 mmol), and K3PO4 (279 mg, 1.31 mmol) in THF (60 mL) gave
17 mg (0.026 mmol, 40%) of the title compound. Rf =0.4 (CH2Cl2/n-
hexane=1:1, v/v); m.p.>3008C; 1H NMR (400 MHz, CDCl3, 258C,
ACHTUNGTRENN(UNG n-pentyl)porphyrin (58): By following
nitrophenylboronic acid pinacol ester (74 mg, 0.3 mmol), [PdACHTNUTRGNE(UNG PPh3)4]
(3.4 mg, 0.003 mmol), and K3PO4 (125 mg, 0.59 mmol) in THF gave
13 mg (0.017 mmol, 56%) of the title compound. Rf =(CH2Cl2/n-
hexane=1:1, v/v); m.p.>3008C; 1H NMR (400 MHz, CDCl3, 258C,
AHCTUNGTRENNUNG
3
TMS): d=ꢀ2.78 (s, 2H, NH), 4.02 (s, 6H, OCH3), 7.69 (t, J=8.2, 7.6 Hz,
3
3
ꢀ
ꢀ
ꢀ
2H, Ar H), 7.82 (t, J=7.6 Hz, 4H, Ar H), 8.42 (d, J=8.8 Hz, 4H, Ar
3
3
NH), 1.01 (t, 3J=7 Hz, 6H,
ꢀ
H), 8.67 (d, J=8.2 Hz, 4H, Ar H), 8.77 (d, J=4.7 Hz, 2H, Hb), 8.81 (s,
2H, Hb), 8.94 (s, 2H, Hb), 8.98 ppm (d, 3J=4.7 Hz, 2H, Hb); 13C NMR
(150 MHz, CDCl3, 258C, TMS): d=55.08, 113.20, 116.74, 120.75, 121.73,
126.97, 127.47, 134.64, 142.46, 147.34, 148.43, 157.56 ppm; UV/Vis
(DMF): lmax (lg e)=421 (4.89), 516 (3.58), 551 (3.36), 592 (3.28), 655 nm
(3.48); HRMS (MS ES+): m/z: calcd for [C46H33N6O6]: 765.2462 [M+H]+
; found 765.2495.
TMS): d=ꢀ2.70 (s, 2H,
2
CH2CH2CH2CH2CH3), 1.28 (m, 4H, CH2CH2CH2CH2CH3), 1.83 (m, 4H,
CH2CH2CH2CH2CH3), 2.58 (m, 4H, CH2CH2CH2CH2CH3), 5.03 (t, 3J=
8.2 Hz, 4H, CH2CH2CH2CH2CH3), 8.08 (d, J=8.2 Hz, 4H, Ar H), 8.31
3
ꢀ
3
3
ꢀ
(d, J=8.2 Hz, 4H, Ar H), 8.67 (s, 2H, Hb), 8.77 (d, J=4.7 Hz, 2H, Hb),
9.52 (d, 3J=4.7 Hz, 2H, Hb), 9.62 ppm (s, 2H, Hb); 13C NMR (150 MHz,
CDCl3, 258C, TMS): d=13.71, 22.33, 29.27, 32.30, 35.29, 38.28, 111.37,
115.77, 118.62, 121.10, 130.09, 134.46, 146.69 ppm; UV/Vis (DMF): lmax
(lg e)=419 (4.97), 517 (3.75), 552 (3.58), 592 (3.27), 650 nm (3.41);
HRMS (MS ES+): m/z: calcd for [C44H41N6]: 653.3393 [M+H]+; found
653.3382.
5,10-Bis(2,6-difluorophenyl)-15,20-bis(4-methoxycarbonylphenyl)porphy-
rin (54): By following the general procedure F, compound 38 (20 mg,
0.028 mmol), 4-methoxycarbonylphenylboronic acid (63 mg, 0.35 mmol),
[PdACHTUNGTRENNUNG(PPh3)4] (3.2 mg, 0.003 mmol), and K3PO4 (154 mg, 0.722 mmol) in
Chem. Eur. J. 2011, 17, 13562 – 13573
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
13571

M. O. Senge et al.
5,10-Bis(4-nitrophenyl)-15,20-di
the general procedure F, compound 39 (40 mg, 0.065 mmol), 4-nitrophen-
yl boronic pinacol ester (161 mg, 0.65 mmol), [Pd(PPh3)4] (7.5 mg,
G
(3.55); HRMS (MS ES+): m/z: calcd for [C44H45N6O4]: 721.3502 [M+H]+
; found 721.3520.
(5,10-Diformyl-15,20-diphenylporphyrinato)copper(II) (70):
A 100 mL
0.007 mmol), and K3PO4 (279 mg, 1.31 mmol) in THF (60 mL) gave
22 mg (0.031 mmol, 47%). Rf =0.59 (CH2Cl2/n-hexane=1:1, v/v); m.p.>
3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.67(s, 2H, NH),
1.02 (t, 3J=7.6, 7 Hz, 6H, CH2CH2CH2CH2CH3), 1.30 (m, 4H,
CH2CH2CH2CH2CH3), 1.83 (m, 4H, CH2CH2CH2CH2CH3), 2.58 (m, 4H,
CH2CH2CH2CH2CH3), 5.03 (t, 3J=8.2 Hz, 4H, CH2CH2CH2CH2CH3),
three-necked flask equipped with a reflux condenser containing anhy-
drous DMF (75 equiv) was charged dropwise and slowly with POCl3
(74 equiv) at 0–28C under an argon atmosphere. After 20 min the
POCl3–DMF complex solidified. After removal of the ice bath, 1,2-di-
chloroethane (5 mL) was added and the solution was heated gently to
508C. Compound 69 was added slowly at 508C as a solution in 1,2-di-
chloroethane (25 mL). After complete addition the mixture was heated
to 908C for 12 h. After the mixture had cooled down in an ice bath, a sa-
turated aqueous sodium-acetate solution was added very carefully and
then the mixture was heated to 808C for 3 h to complete the hydrolysis.
After cooling to RT, the porphyrin was extracted into CH2Cl2 (3ꢅ), fol-
lowed by washing once with water, twice with aqueous NaHCO3, and
then finally twice with brine. Finally, the organic phase was dried with an-
hydrous Na2SO4 and the solvent was evaporated under reduced pressure.
After column chromatography on silica gel (h=46 cm, ø=3 cm) with
CH2Cl2 the first fraction with pure product was obtained as dark-green
crystals after recrystallization from CH2Cl2/MeOH (45.1 mg, 0.077 mmol,
77%). Rf =0.4 (CH2Cl2/n-hexane=3:1, v/v); m.p. 2208C; UV/Vis
(CH2Cl2): lmax (lg e)=432 (4.45), 562 (3.50), 602 nm (3.43); MS (EI,
70 eV): m/z (%): 581 (4, [M]+), 552 (1, [MꢀCHO]+), 523 (2,
[MꢀC2H2O2]+), 445 (2, [MꢀC2H2O2ꢀC6H6]+); HRMS: m/z: calcd for
[C34H22N4O2Cu]: 581.1039 [M+2H]2+; found 581.1042.
3
3
ꢀ
ꢀ
8.36 (d, J=8.7 Hz, 4H, Ar H), 8.65 (d, J=8.2 Hz, 4H, Ar H), 8.69 (s,
2H, Hb), 8.78 (d, 3J=4.7 Hz, 2H, Hb), 9.53 (d, 3J=4.7 Hz, 2H, Hb),
9.62 ppm (s, 2H, Hb); 13C NMR (150 MHz, CDCl3, 258C, TMS): d=
13.71, 29.1, 32.31, 35.31, 38.30, 115.33, 121.44, 134.59, 147.23, 148.66 ppm;
UV/Vis (DMF): lmax (lg e)=420 (4.90), 517 (3.73), 554 (3.45), 594 (3.15),
651 nm (3.33); HRMS (MS ES+): m/z: calcd for [C42H41N6O4]: 693.3189
[M+H]+; found 693.3160.
5,10-Di
following the general procedure F, compound 40 (25 mg, 0.04 mmol), 4-
methoxyphenylboronic acid (72 mg, 0.4 mmol), [Pd(PPh3)4] (4.6 mg,
ACHTUNGTRENNUNG(n-hexyl)-15,20-bis(4-methoxycarbonylphenyl)porphyrin (60): By
AHCTUNGTRENNUNG
0.004 mmol), and K3PO4 (169 mg, 0.8 mmol) in THF gave 10 mg
(0.013 mmol, 34%) of the title compound. Rf =0.54 (CH2Cl2/n-hexane=
1:1, v/v); m.p.>3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS) d=
ꢀ2.68 (s, 2H, NH), 0.96 (t, 3J=7.6 Hz, 6H, CH2CH2CH2CH2CH2CH3),
1.42
(m,
4H,
CH2CH2CH2CH2CH2CH3),
1.54
(m,
4H,
CH2CH2CH2CH2CH2CH3), 1.85 (m, 4H, CH2CH2CH2CH2CH2CH3), 2.56
(m, 4H, CH2CH2CH2CH2CH2CH3), 4.14 (s, 6H, OCH3), 5.03 (t, 3J=8.9,
X-ray single crystal structure determination of 29: The crystals were
grown and handled according to the concept developed by Hope.[36] In-
tensity data were collected at 118 K with a Rigaku CCD system utilizing
MoKa radiation (l=0.71073 ꢄ). The intensities were corrected for Lor-
entz polarization and extinction effects. The structure was solved with
direct methods by using the SHELXTL PLUS program system and re-
fined against |F2| with the program XL from SHELX-97 by using all
data.[37] Nonhydrogen atoms were refined with anisotropic thermal pa-
rameters. Hydrogen atoms were placed into geometrically calculated po-
3
ꢀ
7.6 Hz, 4H, CH2CH2CH2CH2CH2CH3), 8.28 (d, J=8.2 Hz, 4H, Ar H),
3
3
ꢀ
8.45 (d, J=8.2 Hz, 4H, Ar H), 8.71 (s, 2H, Hb), 8.83 (d, J=4.7 Hz, 2H,
Hb), 9.49 (d, 3J=4.7 Hz, 2H, Hb), 9.61 ppm (s, 2H, Hb); 13C NMR
(150 MHz, CDCl3, 258C, TMS): d=13.68, 22.27, 24.91, 28.90, 29.62,
31.46, 35.41, 38.46, 51.93, 119.47, 127.49, 134 ppm; UV/Vis (DMF): lmax
(lg e)=416 (4.96), 518 (3.86), 552 (3.66), 598 (3.47), 655 nm (3.56);
HRMS (MS ES+): m/z: calcd for [C48H51N4O4]: 747.3910 [M+H]+; found
747.3907.
ꢀ
sitions and refined with a ridging model. The N H hydrogen atoms were
5,10-Bis(4-cyanophenyl)-15,20-di
the general procedure F, compound 40 (30 mg, 0.047 mmol), 4-cyanophe-
nylboronic acid (69 mg, 0.47 mmol), [Pd(PPh3)4] (5.4 mg, 0.005 mmol),
ACHTUNGTRENN(UNG n-hexyl)porphyrin (61): By following
refined as disordered over all four positions with occupancies of 50%
each. CCDC-829928 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif. Crystal data: C34H24Br2N4. FW=648.39, red parallel-piped
crystals from CH2Cl2/CH3OH, crystal size 0.5ꢅ0.3ꢅ0.2 mm, monoclinic,
C2/c, a=30.27(2), b=12.148(7), c=15.884(10) ꢄ, b=111.123(14)8, V=
AHCTUNGTRENNUNG
and K3PO4 (200 mg, 0.942 mmol) in THF gave 13 mg (0.019 mmol, 40%)
of the title compound. Rf =0.2 (CH2Cl2/n-hexane=1:1, v/v); m.p.>
3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=ꢀ2.66 (s, 2H, NH),
0.96 (t, 3J=7.6, 7 Hz, 6H, CH2CH2CH2CH2CH2CH3), 1.43 (m, 4H,
CH2CH2CH2CH2CH2CH3), 1.54 (m, 4H, CH2CH2CH2CH2CH2CH3), 1.85
5448(6) ꢄ3, Z=8,
d , mACHTUTGNERNNGU , min/max
calcd =1.58 Mgmꢀ3 (MoKa)=3.008 mmꢀ1
(m,
4H,
CH2CH2CH2CH2CH2CH3),
2.55
(m,
4H,
7.6 Hz,
transmission=0.315/0.585, qmax =31.248, 21370 reflections collected, 4765
independent reflections, Rint =0.1081, 3368 reflections with I>2.0s(I),
364 parameters, R1 (I>2.0s(I))=0.0757, R1 (all data)=0.1092, wR2 (all
data)=0.2168, S=1.042, 1max =1.744 eꢄꢀ3 (near Br atoms).
CH2CH2CH2CH2CH2CH3),
5.04
(t,
4H,
3J=8.2,
CH2CH2CH2CH2CH2CH3), 8.09 (d, 4H, 3J=8.2 Hz, Ar-H), 8.32 (d, 3J=
8.2 Hz, 4H, Ar H), 8.67 (s, 2H, Hb), 8.77 (d, 3J=4.7 Hz, 2H, Hb), 9.52
ꢀ
(d, 3J=4.7 Hz, 2H, Hb), 9.63 ppm (s, 2H, Hb); 13C NMR (150 MHz,
CDCl3, 258C, TMS): d=14.06, 22.66, 31.91, 35.70, 39.09, 112.11, 115.83,
119.11, 121.64, 130.59, 134.89, 147.13, 148.08 ppm; UV/Vis (DMF): lmax
(lg e)=418 (4.87), 517 (4.53) 551 (3.43), 592 (3.13), 650 nm (3.31);
HRMS (MS ES+): m/z: calcd for [C46H45N6]: 681.3706 [M+H]+; found
681.3710.
Acknowledgements
This work was supported by a grant from Science Foundation Ireland
(P.I. 09/IN.1/B2650). We thank Frontier Scientific for generously supply-
ing boronic acids and esters.
5,10-Di
general procedure F, compound 40 (33 mg, 0.047 mmol), 4-nitrophenyl
boronic pinacol ester (117 mg, 0.47 mmol), [Pd(PPh3)4] (5.4 mg,
ACHTUNGTRENNUNG(n-hexyl)-15,20-bis(4-nitrophenyl)porphyrin (62): By following the
AHCTUNGTRENNUNG
0.005 mmol), and K3PO4 (200 mg, 0.942 mmol) in THF (60 mL) gave
20 mg (0.027 mmol, 59%) of the title compound. Rf =0.6 (CH2Cl2/n-
hexane=1:1, v/v); m.p.>3008C; 1H NMR (600 MHz, CDCl3, 258C,
TMS): d=ꢀ2.66 (s, 2H, NH), 0.98 (t, 3J=7.3 Hz, 6H,
CH2CH2CH2CH2CH2CH3), 1.44 (m, 4H, CH2CH2CH2CH2CH2CH3), 1.56
[1] E. Vogel, M. Kocher, H. Schmickler, J. Lex, Angew. Chem. 1986, 98,
262–264; Angew. Chem. Int. Ed. Engl. 1986, 25, 257–259.
[2] a) J. L. Sessler, S. Camiolo, P. A. Gale, Coord. Chem. Rev. 2003, 240,
17–55; b) A. Baeyer, Ber. Dtsch. Chem. Ges. 1886, 19, 2184–2185;
c) J. L. Sessler, D. Seidel, Angew. Chem. 2003, 115, 5292–5333;
Angew. Chem. Int. Ed. 2003, 42, 5134–5175; Angew. Chem. 2003,
115, 5292–5333; d) S. Saito, A. Osuka, Angew. Chem. Int. Ed. 2011,
(m,
4H,
CH2CH2CH2CH2CH2CH3),
1.85
(m,
4H,
CH2CH2CH2CH2CH2CH3), 2.58 (m, 4H, CH2CH2CH2CH2CH2CH3), 5.02
(t, 3J=8.1 Hz, 4H, CH2CH2CH2CH2CH2CH3), 8.36 (d, 3J=8.1 Hz, 4H,
3
Ar H), 8.65 (d, J=8.1 Hz, 4H, Ar H), 8.69 (s, 2H, Hb), 8.78 (d, 3J=
4.7 Hz, 2H, Hb), 9.52 (d, 3J=4.7 Hz, 2H, Hb), 9.62 ppm (s, 2H, Hb);
13C NMR (150 MHz, CDCl3, 258C, TMS): d=22.63, 30.22, 31.81, 35.73,
38.95, 115.72, 121.70, 122.07, 134.88, 135.02, 147.77, 149.37 ppm; UV/Vis
(DMF): lmax (lg e)=421 (5.02), 519 (3.89), 554 (3.76), 595 (3.47), 652 nm
ꢀ
ꢀ
´
50, 4342–4373; Angew. Chem. 2011, 123, 4432–4464; e) M. Ste˛pien,
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N. Sprutta, L. Latos- Graz˙ynski, Angew. Chem. Int. Ed. 2011, 50,
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[3] The “ABCD” nomenclature was suggested by Lindsey and uses cap-
ital letters to denote the arrangement and type of individual meso
13572
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Chem. Eur. J. 2011, 17, 13562 – 13573

Porphyrins with Realigned Dipole Moment
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Received: June 22, 2011
Published online: October 31, 2011
Chem. Eur. J. 2011, 17, 13562 – 13573
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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