Phthalocyanine analogues: Unexpectedly facile access to non-peripherally substituted octaalkyl tetrabenzotriazaporphyrins, tetrabenzodiazaporphyrins, tetrabenzomonoazaporphyrins and tetrabenzoporphyrins

Article abstract of DOI:10.1002/chem.201002176

Controlled syntheses of phthalocyanine/benzoporphyrin hybrid structures have been achieved. We report a simple means for obtaining non-peripherally octaalkyl-substituted derivatives of tetrabenzotriazaporphyrin (TBTAP), tetrabenzodiazaporphyrin (TBDAP), t

Full text of DOI:10.1002/chem.201002176

DOI: 10.1002/chem.201002176
Phthalocyanine Analogues: Unexpectedly Facile Access to Non-Peripherally
Substituted Octaalkyl Tetrabenzotriazaporphyrins,
Tetrabenzodiazaporphyrins, Tetrabenzomonoazaporphyrins and
Tetrabenzoporphyrins
Andrew N. Cammidge,* Isabelle Chambrier, Michael J. Cook,* David L. Hughes,
Muhibur Rahman, and Lydia Sosa-Vargas[a]
Abstract: Controlled syntheses of
phthalocyanine/benzoporphyrin hybrid
structures have been achieved. We
report a simple means for obtaining
non-peripherally octaalkyl-substituted
derivatives of tetrabenzotriazaporphyr-
in (TBTAP), tetrabenzodiazaporphyrin
(TBDAP), tetrabenzomonoazaporphyr-
in (TBMAP) and tetrabenzoporphyrin
(TBP) macrocycles by treating 3,6-dia-
lkyl phthalonitriles with differing
amounts of the Grignard reagent
MeMgBr. This range of macrocyclic
products is not obtained from corre-
sponding reactions of a Grignard re-
agent with 4-substituted phthalonitriles,
reported previously, or reaction of
MeMgBr with a 4,5-dialkyl phthaloni-
trile. Attempts to form a meso-substi-
tuted TBTAP from 3,6-dialkyl phthalo-
nitriles by reaction with benzyl and
long-chain alkyl Grignard reagents un-
expectedly gave only the parent macro-
cycle unsubstituted at the meso posi-
tion. The synthetic protocols are by far
the most straightforward and conven-
ient means to access these interesting,
but scarcely studied, classes of materi-
al. The new series of substituted mac-
rocyclic compounds, obtained as the
metal-free and magnesium- and cop-
per(II)-metallated derivatives, show
trends in the UV/Vis spectra consistent
with those predicted elsewhere by Ko-
bayashi. Characterisation of the new
families allows further trends to be
identified as meso-nitrogen atoms are
sequentially replaced by methine
bridges, for example, the compounds
provide novel examples of macrocyclic
structures that show columnar meso-
phase behaviour. Single-crystal X-ray
structure determinations have been ob-
tained for three magnesium-metallated
derivatives bearing eight hexyl sub-
stituents and constitute the first set of
structural data obtained for such a
series.
Keywords: hybrids · organic mate-
rials · phthalocyanines · porphyri-
noids · synthetic methods
Introduction
contributed much to developing the range of Pc derivatives
known today. Apart from varying the metal or metalloid at
the centre of the ring system, the incorporation of substitu-
ents onto the benzenoid rings, ring annulation and replace-
ment of the benzenoid rings by heteroaromatic units have
provided extraordinary diversification.[5,6] In contrast, TBPs
are less well studied and indeed are significantly less readily
accessible than Pcs. However, increasing recent interest has
been focusing on both the development of new synthetic
routes to TBPs[7] and the exploration of properties for po-
tential applications in, for example, organic electronics, bio-
medical imaging and therapies.[8]
The potentially interesting hybrid structures of the Pc and
TBP macrocycles are those that have a combination of aza
and methine links within the eighteen-p-electron core that
provides the central cavity. However, such macrocycles—
namely, tetrabenzotriazaporphyrins (TBTAPs), tetrabenzo-
diazaporphyrins (TBDAPs) and tetrabenzomonoazapor-
phyrins (TBMAPs)—have received relatively limited atten-
tion. The comprehensive review of the literature concerning
these compounds prior to approximately 2002 by Kobaya-
shi[5] recorded about 50 examples and these included differ-
ently metallated derivatives of the same ligand. Most re-
Phthalocyanines (Pcs) and tetrabenzoporphyrins (TBPs) are
structurally related macrocycles. The former came to promi-
nence in the late 1920s and their basic chemistry was investi-
gated by Linstead and others in the 1930s.[1] Perhaps best
known as commercially important dyes and pigments, Pcs
are now also recognised to constitute a significant class of
functional materials.[2] Their photophysical, electrochemical
and electrical properties are currently exploited in areas as
diverse as photodynamic therapy,[3] security printing, optical
data storage and electrophotography.[4] These advances have
been enabled in part through synthetic chemistry, which has
[a] Dr. A. N. Cammidge, Dr. I. Chambrier, Prof. M. J. Cook,
Dr. D. L. Hughes, Dr. M. Rahman, L. Sosa-Vargas
School of Chemistry, University of East Anglia
Norwich, NR4 7TJ (UK)
E-mail: a.cammidge@uea.ac.uk
Supporting information for this article (containing Table S1: Compa-
rative H NMR data for the methine and aromatic proton signals, and
Figure S1: Further UV/Vis spectra of the metal-free compounds (b
series) and copper-metallated compounds (c series) is available on
the WWW under http://dx.doi.org/10.1002/chem.201002176.
1
3136
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3136 – 3146

FULL PAPER
ports, going back to the 1930s, concern the synthesis of un-
substituted macrocycles by using a mixture of phthalonitrile
and phthalimidine acetic acid[9] or the reaction of methyl
magnesium iodide or methyllithium with phthalonitrile.[10]
More recently, a number of TBTAP derivatives with sub-
stituents such as alkoxy,[11] alkyl[12] or phenyl[13] groups at the
meso position (i.e., at the methine CH) have been de-
scribed. Most routes to these derivatives exploit the reaction
of 1,3-diimino isoindoline with aliphatic carboxylic acids in
the presence of a metal as template agent. Application of
similar routes, which use a suitably substituted precursor,
have afforded derivatives with a substituent located on each
of the benzenoid units, usually at a b-position of the point of
benzofusion.[14] Treatment of 4-substituted phthalonitriles
with a long alkyl chain Grignard reagent provides deriva-
tives substituted at both the b-sites of the benzenoid rings
and at the meso positions.[15,16] Lukyanets and co-workers
obtained tert-butylated TBDAPs and TBMAPs among con-
densation products from potassium tert-butyl phthalimide,
malonic acid, phthalimide and a bis-isoindoline.[17] Subse-
quently, Galanin, Shaposhnikov and co-workers accessed
various examples of meso-substituted derivatives of both
TBDAPs and TBMAPs by using diimino isoindolines as a
precursor.[11,13,15,18]
Our current interest in these hybrid macrocycles was
stimulated by the unexpected formation of a TBTAP during
a
LiOPentyl-induced cyclotetramerisation of 3,6-dihexyl
phthalonitrile (1), Scheme 1, a reaction designed to form the
correspondingly substituted Pc derivative 2b. By using
excess lithium in pentanol a side-product was isolated after
workup that proved to be the non-peripherally octahexyl-
substituted TBTAP 3b. Labelling experiments with 13C es-
tablished that the methine carbon was derived very predom-
inantly from the hydroxyl bearing carbon atom of the alco-
hol solvent.[19]
In the present paper, we report unexpectedly facile access
to non-peripherally substituted octaalkyl-substituted deriva-
tives of all three hybrid macrocycles that is, the TBTAP, cis-
TBDAP (methine groups adjacent) and TBMAP together
with the TBP derivative, (Scheme 1), by reacting 3,6-dialkyl
phthalonitriles with differing amounts of the Grignard re-
agent MeMgBr. Interestingly, this range of compounds is
Scheme 1. Structures of the precursors 1 and 7 as well as the different
macrocycles.
not obtained from the corresponding reactions of
a
Grignard reagent with 4-substituted phthalonitriles[15] or, as
demonstrated in the present work, from reaction of
MeMgBr and a 4,5-dialkyl phthalonitrile. The non-peripher-
ally substituted macrocycles that are the main topic of this
paper are initially formed as the magnesium-metallated ana-
logues. Demetallation affords the metal-free derivatives. Re-
actions with copper acetate give the copper-containing ana-
logues. UV/Vis absorption spectra are reported and liquid-
crystal behaviour exhibited by the compounds has been ex-
plored. Three examples of the substituted magnesium-metal-
lated compounds, a TBTAP, a TBMAP and a TBP deriva-
tive, have been characterised by single-crystal X-ray crystal-
lography.
Results and Discussion
Synthesis: The initial objective of the synthetic programme
was to develop a protocol to obtain the metal-free TBTAP
derivative 3b by using the Grignard–phthalonitrile method
referred to above.[15] Insofar as MeMgBr is expected to
supply the single methine unit within the core of the
TBTAP ring a trial experiment was undertaken by using a
1:4 ratio of MeMgBr to precursor 1. However, the reaction
failed to yield a macrocyclic product. On the other hand, in-
creasing the equivalents of MeMgBr to a 1:1 ratio of starting
materials gave, on workup, a mixture of green-coloured
products (later identified as hybrid structures) with two
compounds predominating.
Chem. Eur. J. 2011, 17, 3136 – 3146
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3137

A. N. Cammidge, M. J. Cook et al.
Further trial experiments led to a protocol based upon
that reported by Leznoff and McKeown for preparing tetra-
substituted TBTAP derivatives from 4-substituted phthaloni-
triles.[19] Their procedure involved heating the crude isolated
product of the Grignard reaction, undertaken in ether, in
quinoline at 2008C for 24 h. In the present work 3,6-dihexyl
phthalonitrile (1) was treated with various equivalents of
MeMgBr in dry THF under reflux and under a nitrogen at-
mosphere for 30 min, during which the solution darkens to
blue/purple. After removal of the solvent the residue was
taken up in dry quinoline and heated under N2 at 2008C
overnight. The cooled reaction mixture, which typically con-
tained at least two green-coloured components, was filtered
through silica by using MeOH as eluent to remove quinoline
and polar side products. Further elution by using THF sepa-
rated the individual green magnesium-metallated macrocy-
cles, 3a–6a, in amounts that varied with the MeMgBr/1
ratio. For each experiment, the magnesium-metallated mac-
rocycles were individually demetallated by using acetic acid
to form the metal-free analogues 3b–6b (Scheme 2). The
latter were obtained in yields reported in Table 1. Trace
amounts of the corresponding phthalocyanine were some-
times observed.
and co-workers.[20] Increasing the MeMgBr/1 ratio further to
5:1 merely suppressed formation of macrocyclic products.
The metal-free derivatives were converted into the corre-
sponding copper-metallated derivatives, 3c–6c (Scheme 1),
by reaction with copper(II) acetate.
A higher homologue of 1, that is, the didecyl phthaloni-
trile 7, was also treated with two equivalents of MeMgBr.
The resulting crude mixture of magnesium-metallated mac-
rocycles 8a–11a was treated with acetic acid to form a mix-
ture containing the metal-free macrocycle derivatives, 8b–
11b. These were separated chromatographically and the
yields of the isolated products are reported in Table 1. Al-
though conditions were not optimised, it can be seen that
the reaction follows broadly the same trend, providing
access to all hybrid structures and demonstrating the gener-
ality of the protocol within this series.
Chemical characterisation of the four isolated magnesi-
um-metallated macrocycles 3a–6a was undertaken through
1
combinations of MALDI-TOF mass spectrometry, H NMR
spectroscopy and elemental analysis. Each macrocycle gave
MALDI-TOF spectra that show isotopic distributions con-
1
sistent with their structures. The H NMR spectral data (see
the Supporting Information, Table S1), confirmed the as-
signed structures not least through the splitting patterns of
signals in the aromatic region (d=7.6–8.1 ppm) and the inte-
gration of the signal(s) observed for the methine proton(s)
that appear between d=10.8 and 11.5 ppm. The splitting of
the aromatic proton signals was particularly valuable for
identifying the TBDAP derivative 4a as that with the two
CH units adjacent (i.e., cis-TBDAP) within the ring system.
Thus, the spectrum shows only two singlets in the aromatic
region, both for two protons and an AB pattern for the four
remaining aromatic protons. In most experiments 4a was
unaccompanied by the isomeric trans-TBDAP, that is, the
compound in which the methine groups are on opposite
sides of the core. However, in occasional cases this was de-
tected as a very minor side-
Scheme 2. i) Varying equivalents of MeMgBr, followed by separation of
Mg-metallated macrocycles (method 1, see the Experimental Section). ii)
Demetallation by using acetic acid. Method 2 (see the Experimental Sec-
tion) involved demetallation of the mixture of recovered Mg-containing
macrocycles by using acetic acid followed by separation of the metal-free
derivatives.
product by NMR spectroscopy.
Table 1. Yields of the isolated metal-free macrocycles from reactions of 3,6-dialkyl phthalonitriles with differ-
ent equivalents of MeMgBr followed by demetallation of the Mg derivatives.
Starting material Ratio[a] Pc–H2 (yield [%]) TBTAP–H2 cis-TBDAP–H2 TBMAP–H2 TBP–H2
Metal-free and copper-metal-
lated compounds, referred to
above, were also characterised
by satisfactory elemental analy-
ses and further by MALDI-
TOF MS and, except for the
paramagnetic copper-containing
A
N
(yield [%])
ACHTUNGTRENUN(NG yield [%])
1
1
1
1
1
1
7
1:4
1:1
2:1
3:1
4:1
5:1
2:1
nd[b]
2b (trace)
2b (trace)
nd
nd
nd
nd
nd
nd
nd
nd
3b (24)
3b (27)
3b (18)
3b (trace)
nd
4b[c] (14)
4b[c] (9)
4b[c] (8)
4b[c] (trace)
nd
5b (trace)
5b (3)
5b (4)
trace
nd
10b (3)
6b (trace)
6b (1)
6b (12)
6b (1)
11b (1)
1
macrocycles, by H NMR spec-
15b (trace)
8b (13)
9b[d] (5)
troscopy (see the Supporting
Information, Table S1). As ex-
[a] Ratio of Grignard reagent to phthalonitrile. [b] nd=not detected. [c] Trace amounts of trans isomer (see
text) were sometimes observed. [d] Mixture of cis and trans isomers.
1
pected, the H NMR spectra of
the metal-free derivatives 3b–
6b exhibited the same features
The highest yield of TBTAP 3b was obtained by using
two equivalents of MeMgBr and one equivalent of 1, where-
as the TBP derivative 6b was formed when the number of
equivalents of Grignard reagent was raised to four. The
latter reaction thus provides a direct and far simpler alterna-
tive means of accessing 6b than that reported by Matsuzawa
as the spectra for their magnesium-metallated analogues
(Figure 1). The octadecyl metal-free homologues 8b–11b
also gave comparable spectra. However, in this series the
cis-TBDAP isomer 9b was accompanied by significant
amounts of the trans-TBDAP isomer (ratio ꢀ3:1) as calcu-
1
lated from signals in the H NMR spectrum of the mixture.
3138
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3136 – 3146

Phthalocyanine Analogues
FULL PAPER
only the TBTAP compound
that is unsubstituted at the
meso site. This result thus con-
stitutes
a further unexpected
difference in the chemistry and
reactivity of 3,6- and 4,5-dialkyl
phthalonitriles
towards
Grignard reagents. Evidently, in
the case of the reaction of the
3,6-dialkyl
there is
phthalonitrile
remarkable C C
7
À
a
bond cleavage at some point
within the reaction sequence,
possibly arising from the steric
crowding at the meso position
in the final, aromatic macrocy-
cle.
UV/Vis spectroscopy: Despite
the relative paucity of examples
of TBTAPs, TBDAPs and
TBMAPs, there has been keen
interest in their absorption
spectra, not least because of the
different effects arising from
the presence of N and CH links
Figure 1. IH NMR signals for the methine (meso) protons and the aromatic protons of the metal-free macrocy-
cles 3b–6b.
We were unable to separate the isomers by recrystallisation
or chromatography.
It is important to note that the near absence of the corre-
sponding phthalocyanine in the product mixtures reported
in Table 1 contrasts significantly with the results reported by
Leznoff and McKeown[15] for the preparation of meso-sub-
stituted TBTAPs by using 4-substituted phthalonitriles and
various Grignard reagents. Their product mixtures contained
at least 50% phthalocyanine and trace amounts of the
TBDAPs. Lower nitrogen-containing hybrids (TBMAPs and
TBPs) were not observed. In light of their results we under-
took
a
further experiment by using 4,5-bis(2-
nitrile (12) (diastereomeric mixture) as
ethylhexyl)phthalo
ACHTUNGTRENNUNG
precursor (Scheme 3).
Reaction of 12 with two equivalents of MeMgBr gave a
mixture of the magnesium phthalocyanine and TBTAP 13a
in the ratio 4:5, the latter recovered in 27% yield. The
result is broadly in line with the findings of Leznoff and
McKeown[15] and emphasizes an unexpected difference in
reaction outcome of 3,6-dialkyl phthalonitriles and the 4,5-
dialkyl phthalonitrile 12 with MeMgBr.
Scheme 3. Conversion of 4,5-bis(2-ethylhexyl)phthalonitrile (12) into
TBTAP–Mg derivatives 13a and 14a by using i) MeMgBr and
ii) PhCH2MgBr, respectively. The corresponding phthalocyanines (not
shown) were also formed (see text). iii) Acetic acid.
Leznoffꢁs and McKeownꢁs use of benzyl magnesium chlo-
ride and long chain alkyl Grignard reagents (CH3-
ACHTUNGTRENNUNG
within the central cavity and the different symmetries en-
countered within the series. The latter become more com-
plex still on changing from a metallated to a metal-free mac-
rocycle. A number of trends have been identified from pre-
viously available literature data[5] and these have been re-
produced by Pariser–Parr–Pople molecular orbital (MO)
calculations undertaken by Kobayashi.[21] In general, the Q
band, the lowest energy p–p* absorption that occurs in the
visible region of the spectra, shifts to shorter wavelength
CTHUNGTRENNUNG
the meso position of the TBTAP ring. We have shown that
the reaction of the 4,5-dialkyl phthalonitrile 12 with a
benzyl Grignard reagent gave a comparable result in form-
ing 14a. However, reactions of 3,6-didecyl phthalonitrile (7)
with various benzyl and alkyl Grignard reagents yielded
Chem. Eur. J. 2011, 17, 3136 – 3146
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3139

A. N. Cammidge, M. J. Cook et al.
Table 2. UV/Vis absorption data measured in THF.
Compounds lmax [nm] (extinction coefficient, loge)
2a
3a
4a
5a
6a
2b
3b
4b
5b
6b
8b
700, 632
694 (5.16), 671 (4.96), 637 (4.48), 410 (4.89)
662 (5.18), 602 (4.35), 431 (4.97), 403 (4.83)
659 (5.19), 641 (4.91), 608 (4.32), 439 (5.47), 429 (5.2)
641 (5.2), 594 (4.39), 445 (5.85), 420 (4.91)
733 (5.07), 695 (4.99), 663 (4.6), 628 (4.38)
716 (4.96), 675 (4.74), 644 (4.46), 615 (4.26), 361 (4.75)
690 (4.91), 656 (4.86), 600 (4.28), 393 (4.79)
682 (5.03), 638 (4.99), 588 (4.29), 433 (4.96), 413 (5.06)
677 (4.72), 626 (4.81), 441 (5.44), 424 (5.31)
716 (5.03), 675 (4.81), 644 (4.53), 614 (4.33), 403 (4.64), 363
(4.67)
9b[a]
10b
11b
13a
13b
688, 652, 391
681, 636, 412
675 (4.6), 628 (4.75), 443 (5.3), 426 (5.18)
680 (5.49), 659 (5.31), 600 (4.61)
697 (5.2), 655 (4.98), 626 (4.59), 596 (4.33), 387 (4.87)
[a] Mixture of trans and cis isomers.
and lower intensity as the aza links are replaced by methine
units. The present compounds, especially 2–6, which consti-
tute a unique set of similarly substituted compounds, illus-
trate the first point well (see Table 2). In particular, for the
Mg-metallated derivatives (Figure 2), the single Q band for
compounds with D4h symmetry, or the longest wavelength
component of the Q band for the other derivatives, exhibit
the following sequence of shifts: 2a (Pc–Mg) lmax =700, 3a
(TBTAP–Mg) 694, 4a (cis-TBDAP–Mg) 662, 5a (TBMAP–
Mg) 659, 6a (TBP–Mg) 641 nm. The extinction coefficients
for the Pc Q band show little variation. Further examples of
spectra can be found in the Supporting Information, Fig-
ure S1.
Mesophase behaviour: Some disc-shaped molecules are
known to exhibit thermotropic columnar mesophase behav-
iour and long-chain-substituted phthalocyanines were
among some of the early examples reported.[22–24] These in-
clude the phthalocyanines 2b and 2c referred to earlier as
Figure 2. UV/Vis absorption spectra of the magnesium-metallated com-
pounds 2a (Pc), 3a (TBTAP), 4a (cis)-TBDAP, 5a (TBMAP) and 6a
(TBP) in THF. Individual spectra were each normalised against the ab-
sorbance of the most intense band in the spectrum.
well as the octakisACTHUNRTGNEUNG(decyl) analogues 15b and 15c
(Scheme 1). We have now studied the behaviour of the
TBTAP, TBDAP, TBMAP and TBP compounds investigated
in this work and shown that these compounds provide exam-
ples of new series of columnar liquid crystals. The com-
pounds were investigated by a combination of differential
scanning calorimetry (DSC) and polarising optical microsco-
py (POM) and the results for discrete compounds in the
R=hexyl series are summarised in Figure 3. The mesophase
behaviour of the hybrids broadly follows that of the parent
phthalocyanines.[23] In the metal-free series of compounds
2b–6b, the clearing temperatures (mesophase to isotropic
liquid) are essentially the same but crystallisation is sup-
pressed in the hybrid and TBP analogues. The parent Pc,
2b, and TBTAP 3b show a single mesophase whereas two
mesophases are observed for TBMAP 5b and TBP 6b.
Transitions between the mesophases are clearly seen by
POM and DSC, the latter technique showing a very small
transition enthalpy (ꢀ1 JgÀ1). The Cu-metallated series
shows more marked differences, with clearing temperatures
reducing significantly across the series and only narrow
mesoACTHNUTRGNEpNUG hase ranges are observed for TBMAP–Cu 5c and
TBP–Cu 6c. Comparison of the observed textures with
those of the parent Pc indicate that all mesophases are col-
umnar hexagonal.[23] In the octadecyl series the mesophase
behaviour of both metal-free and copper-metallated
TBTAPs is almost identical to that found for the parent oc-
tadecyl Pcs.[23] The magnesium derivatives appear to form
columnar hexagonal mesophases at higher temperatures
than either their metal-free or copper-metallated analogues,
but their behaviour is complicated because X-ray data (see
below) demonstrate that the samples investigated have crys-
tallised with bound solvent molecules which presumably are
lost during thermal treatment.
X-ray crystal structure determinations: Hitherto, we have
reported the single-crystal X-ray structure analysis of the
3140
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3136 – 3146

Phthalocyanine Analogues
FULL PAPER
cules are parallel and each mol-
ecule is coplanar with the four
molecules around it (Figure 5).
One benzo group in each mole-
cule has two hexyl chains in
which the carbon atoms form
planes that are coplanar with
the core plane. The two hexyl
chains on the second benzo
group are rotated about the
À
Ca Cb bonds so that the planes
of the carbon atoms are ap-
proximately perpendicular to
the core plane. The third and
fourth benzo rings are symme-
try related to the first and
second rings. Hence, on adja-
cent benzo rings, in each pair of
hexyl groups there is one in
À
which the C C bonds are paral-
lel and one with them perpen-
dicular to the core plane. Fur-
thermore, pairs of hexyl chains
on neighbouring molecules are
aligned to give a series of four
Figure 3. Thermotropic mesophase behaviour of the octahexyl-substituted compounds. Cr, Colh, Colh’ and I
refer to the crystal state, two separate columnar hexagonal mesophases and the isotropic liquid state, respec-
tively. The photographs show the birefringence textures observed by using POM for the mesophases at the in-
dicated temperatures.
metal-free TBTAP 3b[19] and have showed that the com-
pound was isostructural with the corresponding phthalocya-
nine derivative 2b.[25] The present work has focused on ob-
taining the crystal structures of magnesium-containing mac-
rocycles, three examples of which (3a, 5a and 6a) provided
crystals from THF/MeOH solutions that gave diffraction
data suitable for analysis.
In all three crystals, the Mg atom lies on a crystallograph-
ic centre of symmetry and is coordinated to two molecules
of THF. In the case of the TBTAP 3a (Figure 4, top) the ar-
rangement of the hexyl chains is varied and somewhat remi-
niscent of the organisation found earlier for 3b. On each
benzene ring of 3a, there is one hexyl group with a coplanar
(parallel) carbon-atom chain; the second hexyl chain, how-
ever, is either twisted twice so that its carbon atoms do not
have an extended planar shape, or is turned at the Ca atom
and directed out of the molecular plane. The cores of all
molecules are parallel and packing is arranged in layers of
coplanar molecules. Contacts with surrounding molecules
are not as regular as in the crystals of 5a and 6a (see below)
and there do not appear to be any points of parallel p···p in-
teractions.
Figure 4. Crystal structure of 3a (top) and 6a (bottom). Nitrogen atoms
appear in black. Partially shaded core atoms in 3a are 75% N and 25%
C. Hydrogen atoms have been omitted for clarity. Thermal ellipsoids are
drawn at the 50% probability level.
Replacement of two or three of the aza linking atoms of
3a with methine groups as in 5a and 6a, respectively, leads
to a quite different solid-state conformation. The crystal
structures of 5a and 6a are isostructural, that is, the mole-
cules have very similar dimensions, conformations, orienta-
tions and packing arrangements. Unlike 3a, the whole mole-
cule of 5a and 6a (Figure 4, bottom) is approximately
planar in the crystal; in both samples, the cores of all mole-
parallel chains (Figure 5). Above and below each molecule,
there are parallel molecules arranged so that the central
cores overlap, at p···p interaction distances, only at the
edges of one pair of benzo rings. The shortest intermolecular
contacts are C(4)···C(4’)=3.521 and C(17)···CACHTNUTRGNE(NUG 16”)=3.783 ꢂ
in 5a as well as 3.504 and 3.765 ꢂ in 6a, correspondingly.
À
Table 3 compares the Mg N distances for 3a, 5a and 6a
and thus, indicates the increase in cavity size as the nitrogen
Chem. Eur. J. 2011, 17, 3136 – 3146
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3141

A. N. Cammidge, M. J. Cook et al.
gives only trace amounts of phthalocyanine, but significant
amounts of the tetrabenzotriazaporphyrin, tetrabenzodiaza-
porphyrin and the tetrabenzoazaporphyrin. Significantly, on
raising the number of equivalents of MeMgBr to four, the
only macrocycle to be obtained was the tetrabenzoporphyrin
derivative in 12% yield, providing a particularly convenient
synthesis of this ring system. Increasing the number of
equivalents of MeMgBr further reduced the formation of
macrocyclic products. The generality of this mode of reac-
tion was confirmed by using 3,6-didecyl phthalonitrile as
precursor.
The unexpected reactivity of 3,6-dialkyl phthalonitriles to-
wards MeMgBr thus provides a convenient access to an un-
expectedly wide range of octaalkyl-substituted macrocycles.
However, a further unpredicted outcome of this type of re-
action occurred upon treating the 3,6-dialkyl phthalonitriles
with benzyl and long-chain alkyl Grignard reagents. Where-
as such reactions gave rise to meso-substituted TBTAPs
upon reaction with 4- and 4,5-substituted alkyl phthaloni-
triles, reactions with 3,6-dialkyl phthalonitrile gave only the
unsubstituted methine derivative of the TBTAP compound,
Figure 5. Molecular packing in a single layer of compound 5a. The mole-
cules are essentially coplanar.
À
indicating that a C C bond cleavage reaction occurs at
some point during the reaction sequence.
À
atoms are replaced by methine units. Increase in the Mg N
Series, such as 2–6, constitute unique sets of similarly sub-
stituted compounds and characterisation of the new families
allows trends to be identified as meso-nitrogen atoms are se-
quentially replaced by methine bridges. For example, UV/
Vis spectra show progressive absorption shifts and compare
well to previous theoretical studies. The new compounds
also provide further examples of macrocycles that show col-
umnar mesophase behaviour. Crystals suitable for X-ray
structure determination were obtained for the magnesium-
metallated TBTAP 3a, TBMAP 5a and TBP 6a allowing
detailed bonding and geometry to be compared.
À
distances is accompanied by an increase in the Mg O dis-
tances between the central metal and the THF ligands. The
data also show that the macrocycles are essentially planar
with the greatest departure from planarity exhibited by
TBTAP 3a.
Table 3. Comparative data for selected dimensions of the molecules, 3a,
5a and 6a.
Dimensions
3a
5a
6a
À
Mg N [ꢂ]
2.0428(19)
2.0438(19)
2.114(17)
4.14(15) and
5.84(14)8
2.078(4)
2.079(4)
2.236(4)
0.8(4) and
3.5(3)8
2.095(7)
2.100(7)
2.243(6)
0.5(5) and
3.3(5)8
À
Mg O [ꢂ]
tilt of
Experimental Section
benzo rings
from the
N4 plane
Equipment: 1H NMR spectra of compounds in either [D6]benzene or
[D8]THF were obtained at 400 MHz by using a Varian Unityplus-400
spectrometer. The residual proton solvent peak ([D6]benzene d=
7.15 ppm, [D8]THF d=3.78 ppm) was used as reference. MALDI-TOF
spectra were measured by using a Shimadzu Biotech MALDI spectrome-
ter. UV/Vis. spectra were measured on a Hitachi U3000 spectrophotome-
ter. Melting points and mesophase transition temperatures were mea-
sured by differential scanning calorimetry at 58CminÀ1 by using a Q20
TA DSC instrument. Polarised light microscopy was undertaken by using
an Olympus BH-2 polarising microscope in conjunction with a Linkam
TMS 92 thermal analyser with a Linkam THM 600 cell. The heating and
Conclusion
Phthalocyanine–porphyrin hybrids are intriguing and poten-
tially important organic materials. They have received only
scarce attention because their synthesis remains challenging.
Previously Leznoff and McKeown established that 4-substi-
tuted phthalonitriles react with various Grignard reagents to
afford a combination of a phthalocyanine, a tetrabenzotria-
zaporphyrin and small amounts of a tetrabenzodiazapor-
phyrin.[15] Herein, we have shown that a 4,5-dialkyl phthalo-
nitrile reacts similarly with two equivalents of MeMgBr. We
have also demonstrated that the full range of hybrid struc-
tures can be obtained, in a controlled manner, from reac-
tions of 3,6-dialkyl phthalonitrile with MeMgBr. Reaction of
3,6-dihexyl phthalonitrile with two equivalents of MeMgBr
cooling rates used were 58CminÀ1
.
Crystal structure analyses
Crystal data for compound 3a: C89H129MgN7O2; M=1353.3; triclinic;
¯
space group P1 (no. 2); a=9.2771(2), b=14.5894(3), c=15.7001(4) ꢂ;
a=69.089(2), b=78.781(2), g=89.473(2)8; V=1942.86(8) ꢂ3; Z=1;
1calcd =1.157 gcmÀ3; F (MoKa)=0.8 cmÀ1; 29471 total reflec-
ACTHNUTRGENN(UG 000)=740; mACHUTNGTRENNGUN
tions recorded to qmax =238; 5374 unique reflections (Rint =0.075); 3797
“observed” reflections with I>2s(I); final wR2 =0.113 and R1 =0.097
(2B) for all data; R1 =0.052 for the “observed” data.
Crystal data for compound 5a: C91H131MgN5O2; M=1351.3; triclinic;
¯
space group P1 (no. 2); a=9.8500(4), b=11.6803(4), c=17.8281(7) ꢂ;
3142
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3136 – 3146

Phthalocyanine Analogues
FULL PAPER
a=78.309(3), b=87.152(3), g=76.938(3)8; V=1956.60(13) ꢂ3; Z=1,
was filtered through silica gel (eluent: methanol) to remove a red/brown
band containing quinoline. The eluent was changed to THF and a green
fraction was obtained. The solvent was removed and the residue was pu-
rified by column chromatography on silica gel to afford the metallated
derivatives that were re-crystallised from THF/MeOH.
1calcd =1.147 gcmÀ3; F (MoKa)=0.7 cmÀ1; 21779 total reflec-
ACHTUNGTRENNUNG(000)=740; mACHUTNGTRENNGUN
tions recorded to qmax =208; 3623 unique reflections (Rint =0.095); 2414
“observed” reflections with I>2s(I); final wR2 =0.183 and R1 =0.140
(2B) for all data; R1 =0.079 for the “observed” data.
1,4,8,11,15,18,22,25-Octakis
AHCTUNGERTGtNNUN riazaporphinato magnesium (3a): The above-described procedure was
ACHTUNGTNER(UNGN hexyl)-tetrabenzoACHTUNGTREG[NNUN b,g,l,q]ACHTUNGTREN[NUNG 5,10,15]-
Crystal data for compound 6a: C92H132MgN4O2; M=1350.3; triclinic;
space group P1 (no. 2); a=9.8137(17), b=11.6676(15), c=
¯
followed by using 3,6-dihexyl phthalonitrile (1) (200 mg, 0.675 mmol) and
a solution of MeMgBr in Et2O (3m, 0.45 mL, 2 equiv). The residue was
purified by column chromatography on silica gel (dichloromethane). The
desired product eluted as the first green band. Dark blue crystals of 3a
were obtained after re-crystallisation (55 mg, 24%). Transition tempera-
tures: 245.1 (K–D), 300.68C (D–I); 1H NMR (400 MHz, [D6]benzene):
d=11.3 (s, 1H), 8.03 (d, J=8 Hz, 2H), 8.0 (d, J=8 Hz, 2H), 7.99 (d, J=
8 Hz, 2H), 7.91 (d, J=8 Hz, 2H), 5.1 (t, J=6.8 Hz, 4H), 5.04 (t, J=
6.8 Hz, 8H), 4.35 (t, J=6.8 Hz, 4H), 2.45–3.15 (m, 16H), 1.75–1.93 (m,
16H), 1.23–1.48 (m, 32H), 0.82–0.95 ppm (m, 24H); MS (MALDI-TOF):
m/z (%): isotopic cluster at 1208.9 [M+] (100); UV/Vis (THF): lmax
(loge)=694 (5.16), 671 (4.96), 637 (4.48), 410 nm (4.89); elemental analy-
sis calcd for C81H113N7Mg [M+2C4H8O] (%): C 78.99, H 9.61, N 7.24;
found: C 79.07, H 9.58, N 7.19.
17.788(3) ꢂ;a=78.644(12),
b=86.907(13),
g=76.936(13)8;
V=
1945.1(5) ꢂ3; Z=1; 1calcd =1.153 gcmÀ3; F
A
A
;
14301 total reflections recorded to qmax =208; 3597 unique reflections
(Rint =0.187); 1635 “observed” reflections with I>2s(I); final wR2 =0.229
and R1 =0.236 (2B) for all data; R1 =0.113 for the “observed” data.
CCDC-785360 (3a), CCDC-785361 (5a) and CCDC-785362 (6a) contain
the supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
For each sample, a crystal was mounted in oil on a glass fibre and fixed
in the cold nitrogen stream on an Oxford Diffraction Xcalibur-3 CCD
diffractometer equipped with a MoKa radiation source and a graphite
monochromator. Intensity data were measured at 140 K by thin-slice w
and f scans. Data were processed by using the CrysAlisPro-CCD and
-RED[26] programs. Structures were determined by direct methods rou-
tines in SHELXS,[27] and refined by full-matrix least-squares methods, on
F2, in SHELXL.[27] Non-hydrogen atoms were generally refined with ani-
sotropic thermal parameters. In 6a, some of the porphyrin core atoms
were refined isotropically. Hydrogen atoms were included in idealised
positions, Uiso values set to ride on Ueq values of parent carbon atoms.
1,4,8,11,15,18,22,25-Octakis
ACHUTNGTRENNUG(hexyl)-tetrabenzoACHTUNGTRNE[NUGN b,g,l,q]-
AHCTUNGTERG[NNUN 5,10]diazaporphinato magnesium (4a): Further chromatographic separa-
tion of the reaction product described above afforded 4a as the second
green band to be eluted. Recrystallisation gave the product as a green
powder (15.2 mg, 9%). Transition temperatures: 267.6 (K–D) 306.68C
(D–I); 1H NMR (400 MHz, [D6]benzene): d=11.39 (s, 2H), 8.05 (s, 2H),
8.03 (d, J=7.6 Hz, 2H), 7.95 (d, J=7.6 Hz, 2H), 7.82 (s, 2H), 5.17 (t, J=
6.4 Hz, 4H), 5.11 (t, J=6.4 Hz, 4H), 4.37–4.43 (m, 8H), 2.45–2.55 (m,
16H), 1.7–1.9 (m, 16H), 1.25–1.47 (m, 32H), 0.77–0.95 ppm (m, 24H);
MS (MALDI-TOF): m/z (%): isotopic cluster at 1207.9 [M+] (100); UV/
Vis (THF): lmax (THF, loge) = 662 (5.18), 602 (4.35), 431 (4.97), 403 nm
(4.83); elemental analysis calcd for C82H114N6Mg (%): C 81.52, H 9.51, N
6.96; found: C 81.66, H 9.43, N 6.81.
In 3a and 5a, the core N/CH group appears to be disordered around the
ring. Refinement with varying atom site occupations suggests that, in
these (crystallographic) centrosymmetric molecules the CH group is dis-
tributed: in 3a, in an approximate ratio of 7:3 between the two possible
sites N(10) and N(20), with an overall occupancy of one CH per mole-
cule; in 5a, the CH/N group is distributed in an approximate ratio of
75:25 in both the N(10) and N(20) sites, with an overall occupancy of
three CH per molecule.
1,4,8,11,15,18,22,25-OctakisACTHNUTRGENNU(G hexyl)-tetrabenzoHCATUNGTREN[NNGU b,g,l,q][5]azaporphinato
magnesium (5a): Following elution of compounds 3a and 4a from the
product mixture above, the eluent was changed to dichloromethane/THF
50:1. Compound 5a was eluted as the next green band On recrystallisa-
tion dark blue crystals were obtained (7 mg, 3.5%). Transition tempera-
ture: 259.4 (K–D), 309.48C (D–I ); 1H NMR (400 MHz, [D6]benzene):
d=11.7 (s, 1H), 11.57 (s, 2H), 8.11 (d, J=7.6 Hz, 2H), 8.03 (d, J=
7.6 Hz, 2H), 7.97 (d, J=7.6 Hz, 2H), 7.95 (d, J=7.6 Hz, 2H), 5.32 (t, J=
8 Hz, 4H), 4.49–4.62 (m, 12H), 2.5–2.63 (m, 16H), 1.75–1.9 (m, 16H),
1.25–1.47 (m, 32H), 0.85–0.95 ppm (m, 24H); MS (MALDI-TOF) m/z
(%): isotopic cluster at 1206.9 [M+] (100); UV/Vis (THF): lmax (loge)=
659 (5.19), 641 (4.91), 608 (4.32), 439 (5.47), 429 nm (5.2); elemental anal-
ysis calcd for C83H115N5Mg [M+2C4H8O] (%): C 80.88, H 9.77, N 5.18;
found: C 81.0, H 9.62, N 5.06..
Materials and reagents: THF was dried by using Na/benzophenone.
Quinoline was dried over KOH followed by distillation under reduced
pressure. Petroleum ether (b.p. 40–608C) was used. MeMgBr was ob-
tained as a solution in diethyl ether from Aldrich. Chromatographic sepa-
rations were undertaken by column chromatography by using silica gel as
packing agent. The syntheses of 3,6-dihexyl phthalonitrile (1), 3,6-didecyl
phthalonitrile (7),[28] 4,5-bis(2-ethylhexyl)phthalonitrile (12)[29] and the
phthalocyanine derivatives 2b, 2c, 15b and 15c[28] have been described
elsewhere.
Experimental procedures
1,4,8,11,15,18,22,25-OctakisACTHUNRTGNEUNG(hexyl) phthalocyaninato magnesium (2a):
3,6-Dihexyl phthalonitrile (1) (450 mg, 1.5 mmol) was heated in pentanol
(10 mL) in the presence of magnesium acetate tetrahydrate (100 mg, 0.47
mol) and a small piece of magnesium turning. The mixture was heated to
reflux and 1,8-diazabicycloundec-7-ene (DBU) (75 mL, 0.5 mmol) was
added at once. Heating at reflux was continued for 72 h. After cooling,
methanol (10 mL) was added and the blue solid was filtered. The residue
was purified by column chromatography on silica (petroleum ether/
CH2Cl2 1:1). The blue fraction was separated to afford 2a (62 mg, 14%).
1H NMR (400 MHz, [D8]THF): d=7.91 (s, 8H), 4.69 (t, J=6.8 Hz, 16H),
2.19–2.28 (m, 16H), 1.63–1.73 (m, 16H), 1.19–1.48 (m, 32H), 0.8 ppm (t,
J=7 Hz, 24H); UV/Vis (THF): lmax =700, 632 nm; elemental analysis
calcd (%) for C80H113N8Mg: C 79.34, H 9.40, N 9.25; found: C 79.42, H
9.40, N 9.12.
1,4,8,11,15,18,22,25-OctakisACTHNUTRGENNU(G hexyl)-tetrabenzoHCATUNGTREN[NNGU b,g,l,q]porphinato magne-
sium (6a): The general procedure was followed by using 3,6-dihexyl
phthalonitrile (200 mg, 0.675 mmol) and MeMgBr (3m in Et2O, 0.9 mL,
4 equiv). The residue was purified by column chromatography on silica
gel, by using dichloromethane as eluent. After elution of trace amounts
of green products (3a, 4a, 5a) the eluent was changed to dichlorome-
thane/THF (25:1). Compound 6a was eluted as a lighter green band and
was isolated as purple crystals upon recrystallisation (27 mg, 12%). Tran-
sition temperature: 243.9 (K–D), 310.28C (D–I ); 1H NMR (400 MHz,
[D8]THF): d=11.65 (s, 4H), 8.11 (s, 8H), 4.75 (t, J=6.8 Hz, 16H), 2.63–
2.75 (m, 16H), 1.92–2.06 (m, 16H), 1.6–1.71 (m, 16H), 1.48–1.6 (m,
16H), 1.06 ppm (t, J=7 Hz, 24H); MS (MALDI-TOF) m/z (%): isotopic
cluster at 1205.8 [M+] (80); UV/Vis (THF): lmax (loge): 641 (5.2), 594
(4.39), 445 (5.85), 420 nm (4.91); elemental analysis calcd for
C84H116N4Mg [M+2C4H8O] (%): C 81.83, H 9.85, N 4.15; found: C 81.87,
H 9.78, N 4.09.
Magnesium-metallated compounds: The general procedure consists of
dissolving a 3,6-/4,5-dialkyl phthalonitrile (200 mg) in dry THF (3 mL)
under N2. A solution of MeMgBr in Et2O (3m, 1–4 equiv) was added at
once and the mixture was heated to reflux for 30 min. During this time,
the solution darkens to blue/purple. The mixture was cooled to room
temperature and the solvent was removed under reduced pressure. Dry
quinoline (3 mL) was added and the solution was heated under N2 to
2008C overnight. The dark green mixture was cool to RT. The mixture
2,3,9,10,15,16,23,24-Octakis(2-ethylhexyl)-tetrabenzo
ACHTUNGTRENUN[NG b,g,l,q]-
AHCTUNGTRENNUNG
dure was followed by using 4,5-bis(2-ethylhexyl)phthalonitrile (12)
(200 mg, 0.568 mmol) and MeMgBr (3m in Et2O, 0.38 mL, 2 equiv). The
Chem. Eur. J. 2011, 17, 3136 – 3146
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3143

A. N. Cammidge, M. J. Cook et al.
residue was purified by column chromatography on silica gel, by using
petroleum ether/THF 40:1. as eluent. Compound 13a was eluted with the
first green band and was isolated as a green powder after recrystallisation
residue of the reaction was purified by column chromatography, by using
petroleum ether/CH2Cl2 10:1 then 5:1 as eluent Compound 5b was
eluted as a green band and was recrystallised as a green powder in quan-
titative yield. Transition temperature: 155.0 (K–D), 176.98C (D–I);
1H NMR (400 MHz, [D6]benzene): d=10.99 (s, 2H), 10.95 (s, 1H), 7.97
(d, J=7.2 Hz, 2H), 7.86 (d, J=7.2 Hz, 2H), 7.59 (d, J=7.6 Hz, 2H), 7.57
(d, J=7.6 Hz, 2H), 5.05 (t, J=6.8 Hz, 4H), 4.11 (t, J=6.8 Hz, 4H), 4.02
(t, J=6.8 Hz, 4H), 3.92 (t, J=6.8 Hz, 4H), 2.37–2.43 (m, 4H), 2.25–2.31
(m, 4H), 2.1–2.25 (m, 8H), 1.79–1.87 (m, 4H), 1.58–1.68 (m, 12H), 1.27–
1.47 (m, 32H), 0.82–0.93 (m, 24H), À1.29 ppm (s, 2H); MS (MALDI-
TOF) m/z (%): isotopic cluster at 1184.2 [M+] (100); UV/Vis (THF): lmax
(loge)=682 (5.03), 638 (4.99), 588 (4.29), 433 (4.96), 413 nm (5.06); ele-
mental analysis calcd for C83H117N5 (%): C 84.14, H 9.95, N 5.91; found:
C 84.23, H 9.88, N 5.92.
1
(54 mg, 27%). M.p. 284.58C; H NMR (400 MHz, [D8]THF): d=10.61 (s,
1H), 9.31 (s, 2H), 9.27 (s, 2H), 9.26 (s, 2H), 9.17 (s, 2H), 3.12–3.3 (m,
16H), 2.0–2.18 (m, 8H), 1.34–1.8 (m, 64H), 1.0–1.15 (m, 24H), 0.85–
1.0 ppm (m, 24H); MS (MALDI-TOF) m/z (%): isotopic cluster at
1433.5 [M+] (100); UV/Vis (THF): lmax (loge): 680 (5.49), 659 (5.31),
600 nm (4.61); elemental analysis calcd for C97H145N7Mg [M+2C4H8O]
(%): C 79.93, H 10.29, N 6.21; found: C 79.80, H 10.07, N 6.16.
2,3,9,10,15,16,23,24-Octakis(2-ethylhexyl)-27-phenyl-tetrabenzo
ACHTUNGTRENUN[NG b,g,l,q]-
ACHTUNGTRENNUNG[5,10,15]triazaporphinato magnesium (14a): The procedure described
above was followed by using 4,5-bis(2-ethylhexyl)phthalonitrile (200 mg,
0.568 mmol) and BzMgCl (1m in Et2O, 1.2 mL, 2 equiv). The residue was
purified by column chromatography on silica gel, by using petroleum
ether/THF 15:1 as eluent. Compound 14a was eluted as the first green
band (6 mg, 1%). 1H NMR (400 MHz, [D8]THF): d=9.29 (s, 2H), 9.25
(s, 2H), 9.23 (s, 2H), 8.13–8.2 (m, 2H), 8.01–8.09 (m, 1H), 7.92–8.01 (m,
2H), 6.94 (s, 2H), 3.0–3.29 (m, 16H), 1.96–2.17 (m, 8H), 1.25–1.77 (m,
64H), 0.86–1.1 ppm (m, 48H); MS (MALDI-TOF) m/z (%): isotopic
cluster at 1508.32 [M+] (100); UV/Vis (THF): lmax =685, 661 nm.
1,4,8,11,15,18,22,25-OctakisACTHNUTRGENNU(G hexyl)-29H,31H-tetrabenzoACHTUTGNREN[NUGN b,g,l,q]porphine
(6b): The above-described procedure (method 1) was followed to deme-
tallate 6a. The residue was purified by column chromatography, by using
petroleum ether/CH2Cl2 5:1 as eluent Compound 6b was eluted as a
green band and the material was recrystallised to afford a green powder.
Transition temperature: 150.3 (K–D), 178.98C (D–I); 1H NMR
(400 MHz, [D6]benzene): d=11.48 (s, 4H), 7.88 (s, 8H), 4.33 (t, J=
6.8 Hz, 16H), 2.28–2.48 (m, 16H), 1.6–1.85 (m, 16H), 1.2–1.47 (m, 32H),
0.78–0.98 (m, 24H), À2.25 ppm (s, 2H); MS (MALDI-TOF) m/z (%):
isotopic cluster at 1183.27 [M+] (100); UV/Vis (THF): lmax (loge)=677
(4.72), 626 (4.81), 441 (5.44), 424 nm (5.31); elemental analysis calcd for
C84H118N4 (%): C 85.22, H 10.05, N 4.73; found: C 85.13, H 10.14, N 4.80.
Attempted functionalisation of compound 3 at the meso position by cy-
clotetramerisation of phthalonitrile 1 with various Grignard reagents:
The reactions were carried out as stated above to give 3a by using differ-
ent Grignard reagents. In all cases, TBTAP (3a) was obtained exclusively
in the following yields: 18% from ethylmagnesium bromide, 23% from
n-pentylmagnesium bromide, 24% from n-heptylmagnesium bromide,
28% from n-decylmagnesium bromide and 25% from benzylmagnesium
bromide.
Method 2: Demetallation of the product mixture: In a general procedure
3,6-didecylphthalonitrile (7) (200 mg) was dissolved in dry THF (3 mL)
under N2. A solution of MeMgBr in Et2O (3m in Et2O, 1–4 equiv) was
added at once and the mixture was heated at reflux for 30 min. During
this time, the solution darkened to blue/purple. The solution containing a
mixture of the magnesium-metallated compounds, 8a–11a was then
cooled to RT and the solvent was removed under reduced pressure. Dry
quinoline (3 mL) was added and the solution was heated under N2 to
2008C overnight. The dark green mixture was cooled to RT. Acetic acid
(3 mL) was added and the mixture was heated to reflux for 30 min.
Excess methanol was added and the solid residue was filtered and
washed with methanol. The green material was purified by column chro-
matography over silica gel to afford the metal-free derivatives that were
recrystallised from THF/MeOH.
Metal-free compounds
Method 1: Demetallation of individual Mg-metallated macrocycles: The
metallated derivative was heated to reflux in acetic acid (3 mL) for
30 min. After cooling, methanol (5 mL) was added to the suspension and
the green powder was collected by filtration and washed with further
methanol. The compound was then purified by column chromatography
on silica gel to afford the metal-free derivative that was recrystallised
from THF/MeOH.
1,4,8,11,15,18,22,25-Octakis
ACHUTGTNRENNUG(hexyl)-29H,31H-tetrabenzoACHTUNGTERN[NUGN b,g,l,q]-
ACHTUNGTRENNUNG
was followed by using compound 3a. The residue was purified by column
chromatography, by using petroleum ether (b.p. 40–608C) as eluent. The
desired product was eluted as the first green band. Compound 3b was
obtained a green powder in quantitative yield after recrystallisation.
Transition temperature: 150.2 (K–D), 171.18C (D–I); 1H NMR
(400 MHz, [D6]benzene): d=10.69 (s, 1H), 7.86 (s, 4H), 7.84 (d, J=8 Hz,
2H), 7.75 (d, J=8 Hz, 2H), 4.81 (t, J=6.8 Hz, 4H), 4.7 (t, J=6.8 Hz,
8H), 4.05 (t, J=6.8 Hz, 4H), 2.2–2.38 (m, 16H), 1.6–1.8 (m, 16H), 1.2–
1.42 (m, 32H), 0.75–0.91 (m, 24H), À0.31 ppm (s, 2H); MS (MALDI-
TOF) m/z (%): isotopic cluster at 1186.13 [M+] (100); UV/Vis (THF):
lmax (loge)=716 (4.96), 675 (4.74), 644 (4.46), 615 (4.26), 361 nm (4.75);
elemental analysis calcd for C81H115N7 (%): C 80.97, H 9.77, N 8.26;
found: C 81.07, H 9.69, N 8.37.
1,4,8,11,15,18,22,25-Octakis
AHCTUNGTRENNUNG
ACHUTGTNRENNUG(decyl)-29H,31H-tetrabenzoACHTUNGTERN[NUGN b,g,l,q]-
was undertaken by using 3,6-didecylphthalonitrile (200 mg, 0.49 mmol)
and MeMgBr (3m in Et2O, 0.33 mL, 2 equiv). The residue was purified
by column chromatography, by using petroleum ether (b.p. 40–608C) as
eluent. The first fraction that was eluted (green band) afforded com-
pound 8b as a green powder after recrystallisation (26 mg, 13.1%). Tran-
sition temperature: 76.5 (K–D), 139.28C (D–I); 1H NMR (400 MHz,
[D6]benzene): d=10.83 (s, 1H), 7.9 (m, 4H), 7.84 (d, J=7.6 Hz, 2H),
7.74 (d, J=7.6 Hz, 2H), 4.75–4.84 (m, 12H), 4.00 (t, J=7.2 Hz, 4H),
2.26–2.37 (m, 16H), 1.75–1.83 (m, 12H), 1.66–1.72 (m, 4H), 1.1–1.5 (m,
96H), 0.85 (t, J=7.2 Hz, 6H), 0.80–0.85 (m, 18H), À0.37 ppm (s, 2H);
MS (MALDI-TOF) m/z (%): isotopic cluster at 1635.8 [M+] (35); UV/
Vis (THF): lmax (loge)=716 (5.03), 675 (4.81), 644 (4.53), 614 (4.33), 403
(4.64), 363 nm (4.67); elemental analysis calcd for C113H179N7 (%): C
82.98, H 11.03, N 5.99; found: C 83.08, H 10.95, N 5.98.
1,4,8,11,15,18,22,25-Octakis
ACHUTGTNRENNUG(hexyl)-29H,31H-tetrabenzoACHTUNGTERN[NUGN b,g,l,q]-
ACHTUNGTRENNUNG
method 1. The residue of the reaction was purified by column chromatog-
raphy, by using petroleum ether (b.p. 40–608C) as eluent. Compound 4b
was obtained in quantitive yield as a green powder after recrystallisation.
Transition temperature: 164.1 (K–D), 172.38C (D–I); 1H NMR
(400 MHz, [D6]benzene): d=10.98 (s, 2H), 7.9 (s, 2H), 7.86 (d, J=8 Hz,
2H), 7.8 (d, J=8 Hz, 2H), 7.69 (s, 2H), 4.9 (t, J=6.8 Hz, 4H), 4.8 (t, J=
6.8 Hz, 4H), 4.04–4.15 (m, 8H), 2.21–2.36 (m, 16H), 1.58–1.8 (m, 16H),
1.12–1.45 (m, 32H), 0.75–0.92 (m, 24H), À0.2 ppm (s, 2H); MS
(MALDI-TOF) m/z (%): isotopic cluster at 1185.45 [M+] (100); UV/Vis
(THF): lmax (loge)=690 (4.91), 656 (4.86), 600 (4.28), 393 nm (4.79); ele-
mental analysis calcd for C82H116N6 (%): C 83.05, H 9.86, N 7.09; found:
C 83.15, H 9.79, N 7.08.
1,4,8,11,15,18,22,25-Octakis
ACHUTGTNRENNUG(decyl)-29H,31H-tetrabenzoACHTUNGTERN[NUGN b,g,l,q]-
A
ACHTUNGTRENNUNG
of the reaction mixture described above, by using petroleum ether as
eluent, afforded a second green band. Isolation and recrystallisation af-
forded compounds as an isomeric mixture, (ratio [5,10]/
obtained by NMR spectroscopy) (16 mg, 4.8%). M.p. 157.98C; 1H NMR
(400 MHz, [D6]benzene): d=11.03 (s, 2H[5,15]), 10.82 (s, 2H[5,10]), 7.97
(s, 2H[5,10]), 7.93–7.95 (m, 4H[5,15]), 7.89 (d, J=7.2 Hz, 2H[5,10]),
7.79–7.82 (m, 2H[5,10]+4H[5,15]), 7.55 (s, 2H[5,10]), 4.85–4.96 (m, 8H-
[5,10]+8H[5,15]), 4.11 (t, J=7.2 Hz, 8H[5,15]), 4.01 (t, J=7.2 Hz, 4H-
[5,10]), 3.93 (t, J=7.2 Hz, 4H[5,10]), 2.18–2.4 (m, 16H[5,10]+16H[5,15]),
1.72–1.87 (m, 8H[5,10]+8H[5,15]), 1.55–1.72 (m, 8H[5,10]+8H[5,15]),
ACHTUNGTREN[NGNU 5,15] 7.25:1 as
A
ACHTUNGTRENNUNG
R
E
ACHTUNGTRENNUNG
R
A
ACHTUNGTRENNUNG
A
U
ACHTUNGTRENNUNG
1,4,8,11,15,18,22,25-Octakis
G
N
R
A
U
ACHTUNGTRENNUNG
phine (5b): Demetallation of 5a was undertaken by using method 1. The
G
A
U
ACHTUNGTRENNUNG
3144
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3136 – 3146

Phthalocyanine Analogues
FULL PAPER
1.1–1.55 (m, 96H
G
E
N
product eluted as a blue band. A blue powder of compound 3c was ob-
tained after recrystallisation (18 mg, 90%). Transition temperature: 206.2
(K–D), 233.18C (D–I); MS (MALDI-TOF) m/z (%): isotopic cluster at
1247.9 [M+] (100); UV/Vis (THF): lmax (loge)=700 (5.5), 675 (5.3), 454,
393, 359 nm; elemental analysis calcd for C81H113N7Cu (%): C 77.93, H
9.12, N 7.85; found: C 78.01, H 8.89, N 7.62.
A
ACHTUNGTRENNUNG
TOF) m/z (%): isotopic cluster at 1635.0 [M+] (50); UV/Vis (THF):
lmax =688, 652, 391 nm; elemental analysis calcd for C114H180N6 (%): C
83.76, H 11.09, N 5.14; found: C 83.79, H 10.99, N 5.12.
1,4,8,11,15,18,22,25-OctakisACTHNUTRGENN(UG decyl)-29H,31H-tetrabenzoACHTUNGTERN[NUGN b,g,l,q][5]azapor-
1,4,8,11,15,18,22,25-Octakis
[5,10]/[5,15]diazaporphinato copper (4c): The above-described procedure
was followed by using 1,4,8,11,15,18,22,25-octakis(hexyl)-tetrabenzo-
[b,g,l,q][5,10]/[5,15]diazaporphyrin (4b) (20 mg, 0.07 mmol) and copper
acetate (20 mg, excess). The residue was purified by column chromatog-
raphy on silica gel, by using petroleum ether/THF 2:1 as eluent. The de-
sired product eluted as a blue band. A blue powder of compound 4c was
obtained after recrystallisation (20 mg, 98%). M.p. 232.58C; MS
(MALDI-TOF) m/z (%): isotopic cluster at 1246.07 [M+] (100); UV/Vis
(THF): lmax =665, 605, 391 nm; elemental analysis calcd for C84H118N4
(%): C 78.96, H 9.21, N 6.74; found: C 79.05, H 9.16, N 6.62.
ACHUTNGTRENNUG(hexyl)-tetrabenzoACHTUNGTRNE[NUGN b,g,l,q]-
phine (10b): The above-described chromatographic separation of prod-
ucts was continued with a change of the eluent to petroleum ether/
CH2Cl2 10:1. Compound 10b was eluted as the next green band and the
recovered material was recrystallised to afford a green powder (5.6 mg,
2.8%). Transition temperature: 87.1 (K–D), 164.28C (I–D); 1H NMR
(400 MHz, [D6]benzene): d=11.13 (s, 1H), 11.11 (s, 2H), 8.01 (d, J=
7.6 Hz), 2H, 7.91 (d, J=7.6 Hz, 2H), 7.73 (d, J=7.6 Hz, 2H), 7.71 (d, J=
7.6 Hz, 2H), 5.08 (t, J=7.2 Hz, 4H), 4.18–4.22 (m, 8H), 4.1 (t, J=7.2 Hz,
4H), 2.28–2.46 (m, 16H), 1.82–1.86 (m, 4H), 1.64–1.8 (m, 12H), 1.16–
1.52 (m, 96H), 0.84–92 (m, 18H), 0.82 (t, J=7.6 Hz, 6H), À1.15 ppm (s,
2H); MS (MALDI-TOF) m/z (%): isotopic cluster at 1633.7 [M+] (70);
UV/Vis (THF): lmax =681, 636, 412 nm; elemental analysis calcd for
C115H181N5 (%): C 84.55, H 11.17, N 4.29; found: C 84.62, H 11.07, N
4.21.
G
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
E
G
ACHTUNGTRENNUNG
1,4,8,11,15,18,22,25-Octakis
copper (5c): The above-described procedure was followed by using
1,4,8,11,15,18,22,25-octakis(hexyl)-tetrabenzo[b,g,l,q][5]azaporphyrin (5b)
ACHUTGTNRNEUG(N hexyl)-tetrabenzoACHUTNGTREN[NGUN b,g,l,q][5]azaporphinato
A
ACHTUNGTRENNUNG
(20 mg, 0.07 mmol) and copper acetate (20 mg, excess). The residue was
purified by column chromatography on silica gel, by using petroleum
ether/THF 2:1 as eluent. The desired product eluted as a blue band. A
blue powder of compound 5c was obtained after recrystallisation (17 mg,
90%). Transition temperature: 200.4 (K–D), 211.08C (D–I); MS
(MALDI-TOF) m/z (%): isotopic cluster at 1245.41 [M+] (100); UV/Vis
(THF): lmax =661, 428, 412 nm; elemental analysis calcd for C83H115N5Cu
(%): C 79.98, H 9.30, N 5.62; found: C 78.71, H 8.58, N 4.82.
1,4,8,11,15,18,22,25-OctakisACTHNUTRGENNU(G decyl)-29H,31H-tetrabenzoACHTUTGNREN[NUGN b,g,l,q]porphine
(11b): Continued chromatographic separation of the above-described
product mixture by changing the eluent to petroleum ether/CH2Cl2 5:1
provided compound 11b as
a green powder after recrystallisation
1
(2.2 mg, 1.1%). M.p. 1728C; H NMR (400 MHz, [D6]benzene): d=11.56
(s, 4H), 7.96 (s, 8H), 4.51 (t, J=7.2 Hz, 16H), 2.49 (m, 16H), 1.81 (m,
16H), 1.22–1.48 (m, 96H), 0.82 (t, J=7.6 Hz, 24H), À1.91 ppm (s, 2H);
MS (MALDI-TOF) m/z (%): isotopic cluster at 1632.5 [M+] (100); UV/
Vis (THF): lmax (loge)=675 (4.6), 628 (4.75), 443 (5.3), 426 nm (5.18); el-
emental analysis calcd for C116H182N4 (%): C 85.33, H 11.24, N 3.43;
found: C 84.97, H 11.02, N 3.19.
1,4,8,11,15,18,22,25-Octakis
(6c): The above-described procedure was followed by using
1,4,8,11,15,18,22,25-octakis(hexyl)-tetrabenzo[b,g,l,q]porphyrin (6b)
ACHUTGTNRNEUG(N hexyl)-tetrabenzoACHUTNGTREN[NGUN b,g,l,q]porphinato copper
A
ACHTUNGTRENNUNG
(20 mg, 0.07 mmol) and copper acetate (20 mg, excess). The residue was
purified by column chromatography on silica gel, by using petroleum
ether/THF 2:1 as eluent. The desired product eluted as a green band. A
green powder of compound 6c was obtained after recrystallisation
(18 mg, 90%). Transition temperature: 184.0 (K–D), 189.28C (D–I); MS
(MALDI-TOF) m/z (%): isotopic cluster at 1244.33 [M+] (100); UV/Vis
(THF): lmax =660, 637, 429 nm; elemental analysis calcd for C84H116N4Cu
(%): C 81.01, H 9.39, N 4.50; found: C 80.93, H 9.39, N 4.50.
2,3,9,10,15,16,23,24-Octakis(2-ethylhexyl)-29H,31H-tetrabenzo
ACHTUNGTRENNUNG
ACHTUNGTRENUN[NG b,g,l,q]-
metallation of the corresponding magnesium derivative 13a by following
method 1. The product was obtained as a green powder after recrystalli-
sation in quantitative yield. M.p. 286.18C; 1H NMR (400 MHz,
[D6]benzene): d=10.59 (s, 1H), 9.83 (s, 2H), 9.76 (s, 4H), 9.11 (s, 2H),
3.12–3.29 (m, 16H), 2.02–2.15 (m, 8H), 1.28–1.71 (m, 64H), 0.91–1.08 (m,
48H), À0.33 ppm (s, 2H); MS (MALDI-TOF) m/z (%): isotopic cluster
at 1410.2 [M+] (100); UV/Vis (THF): lmax (loge)=697 (5.2), 655 (4.98),
626 (4.59), 596 (4.33), 387 nm (4.87) nm; elemental analysis calcd for
C97H147N7 (%): Found (%) C 82.55, H 10.49, N 6.95; found: C 82.45, H
10.47, N 6.97.
1,4,8,11,15,18,22,25-Octakis
[5,10,15]triazaporphinato copper (8c): The above-described procedure
was followed by using 1,4,8,11,15,18,22,25-octakis(decyl)-tetrabenzo-
[b,g,l,q][5,10,15]triazaporphyrin (8b) (20 mg, 0.07 mmol) and copper ace-
ACHUTNGTRENNUG(decyl)-tetrabenzoACHTUNGTRNE[NUGN b,g,l,q]-
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
tate (20 mg, excess). The residue was purified by column chromatography
on silica gel, by using petroleum ether/THF (2:1) as eluent. The desired
product eluted as a blue band. A blue powder of compound 8c was ob-
tained after recrystallisation (20 mg, 97%). Transition temperature: 76.3
(K–D), 195.98C (D–I); MS (MALDI-TOF) m/z (%): isotopic cluster at
[M+] (100); UV/Vis (THF): lmax =700, 675 nm; elemental analysis calcd
for C84H118N4 (%): C 79.97, H 10.51, N 5.78; found: C 80.06, H 10.46, N
5.61.
2,3,9,10,15,16,23,24-Octakis(2-ethylhexyl)-27-phenyl-29H,31H-tetrabenzo-
ACHTUNGTRENNUNG[b,g,l,q]ACHTUNGTRENNUNG[5,10,15]triazaporphine (14b): The title compound was obtained
by demetallation of the corresponding magnesium derivative 14a by fol-
lowing method 1. The residue was purified by column chromatography,
by using petroleum ether/THF 15:1 as eluent. The eluted green fraction
afforded compound 14b (5 mg). 1H NMR (400 MHz, [D6]benzene): d=
9.91 (s, 2H), 9.77 (s, 2H), 9.74 (s, 2H), 7.98–8.05 (m, 2H), 7.7–7.82 (m,
3H), 7.19 (s, 2H), 3.07–3.27 (m, 12H), 2.84–2.91 (m, 4H), 1.96–2.12 (m,
6H), 1.72–1.82 (m, 2H), 1.2–1.72 (m, 64H), 0.86–1.08 ppm (m, 48H); MS
(MALDI-TOF) m/z (%): isotopic cluster at 1487.25 [M+] (100); UV/Vis
(THF): lmax =700, 658, 628, 602 nm.
Acknowledgements
Copper-metallated compounds: The general procedure consists of dis-
solving the pre-formed TBTAP/TBDAP/TBMAP/TBP derivatives in
pentanol. The solution was brought to reflux and copper(II) acetate was
added at once. Heating to reflux was continued for 30 min, and the solu-
tion was then cooled to RT. Methanol was added and the solid was fil-
tered and washed with methanol. The blue powder was then purified by
column chromatography on silica to afford the metallated derivatives
that were recrystallised from THF/MeOH.
We thank the TSB for a consortium grant, Project No. TP/6/EPH/6/S/
K2536J, CONACYT (Mexico) for financial support for L.S.-V., and the
EPSRC Mass Spectrometry Service at Swansea for MALDI-TOF spec-
tral data.
[1] N. B. McKeown, Phthalocyanine Materials: Synthesis Structure and
Function, University Press, Cambridge, 1998.
1,4,8,11,15,18,22,25-Octakis
[5,10,15]triazaporphinato copper (3c): The above-described procedure
was followed by using 1,4,8,11,15,18,22,25-octakis(hexyl)-tetrabenzo-
[b,g,l,q][5,10,15]triazaporphyrin (3b) (20 mg, 0.07 mmol) and copper ace-
ACHUTNGTRENNUG(hexyl)-tetrabenzoACHTUNGTRNE[NUGN b,g,l,q]-
ACHTUNGTRENNUNG
[2] a) Structure and Bonding Vol. 135: Functional Phthalocyanine Mo-
lecular Materials (Ed.: D. M. P. Mingos), Springer, Berlin, 2010;
b) C. G. Claessens, U. Hahn, T. Torres, Chem. Rec. 2008, 8, 75–97.
[3] a) E. Ben-Hur, W-S Chan in The Porphyrin Handbook, Vol. 19
(Eds.: K. M. Kadish, K. M. Smith, R. Guilard), Academic Press,
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
tate (20 mg, excess). The residue was purified by column chromatography
on silica gel, by using petroleum ether/THF 2:1 as eluent. The desired
Chem. Eur. J. 2011, 17, 3136 – 3146
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3145

A. N. Cammidge, M. J. Cook et al.
Boston, 2003, pp. 1–35; b) L. B. Josefsen, R. W. Boyle, Met.-Based
Drugs 2008, 276109.
[13] a) N. E. Galanin, E. V. Kudrik, G. P. Shaposhnikov, Russ. J. Gen.
Chem. 2005, 75, 651–655; b) N. E. Galanin, E. V. Kudrik, G. P. Sha-
poshnikov, Russ. J. Org. Chem. 2002, 38, 1200–1203.
[14] a) Y. B. Ivanova, Y. I. Churakhina, A. S. Semeikin, N. Z. Mamar-
dashvili, Russ. J. Gen. Chem. 2009, 79, 833–838; b) B. Kaletta, M.
Rolf, W. Wolf, D. R. Terrell, D. R. 1992, US005162518A.
[15] C. C. Leznoff, N. B. McKeown, J. Org. Chem. 1990, 55, 2186–2190.
[16] N. E. Galanin, L. A. Yakubov, E. V. Kudrik, G. P. Shaposhnikov,
Russ. J. Gen. Chem. 2008, 78, 1436–1440
[17] E. A. Makarova, V. N. Kopranenkov, V. K. Shevtsov, E. A. Lukya-
nets, Chem. Heterocyc. Compd. 1989, 25, 1159–1164.
[18] N. E. Galanin, G. P. Shaposhnikov, Russ. J. Gen. Chem. 2007, 77,
1951–1954.
[4] a) P. Erk, H. Hengelsberg in The Porphyrin Handbook, Vol. 19
(Eds.: K. M. Kadish, K. M. Smith, R. Guilard), Academic Press,
Boston, 2003, pp. 105–149; b) P. Gregory, J. Porphyrins Phthalocya-
nines 2000, 4, 432–437; c) T. Shima, Y. Yamakawa, T. Nakano, J.
Kim, J. Tominaga, Jpn. J. Appl. Phys. Part 2 2006, 45, L1007–L1009;
d) H. Mustroph, M. Stollenwerk, V. Bressau, Angew. Chem. 2006,
118, 2068–2087; Angew. Chem. Int. Ed. 2006, 45, 2016–2035.
[5] N. Kobayashi in The Porphyrin Handbook, Vol. 15 (Eds.: K. M.
Kadish, K. M. Smith, R. Guilard), Academic Press, Boston, 2003,
pp. 161–262.
[6] P. A. Stuzhin, C. Ercolani in The Porphyrin Handbook, Vol. 15
(Eds.: K. M. Kadish, K. M. Smith, R. Guilard), Academic Press,
Boston, 2003, pp. 263- 364.
[19] A. N. Cammidge, M. J. Cook, D. L. Hughes, F. Neckelson, M.
Rahman, Chem. Commun. 2005, 930–932.
[7] a) N. E. Galanin , L. A. Yakubov, G. P. Shaposhnikov, Russ. J. Org.
Chem. 2009, 45, 1024–1030; b) N. E. Galanin, E. V. Kudrik, G. P.
Shaposhnikov, Russ. Chem. Bull. 2008, 57, 1595–1610; c) N. E. Gala-
nin, L. A. Yakubov, G. P. Shaposhnikov, Russ. J. Gen. Chem. 2008,
78, 1802–1807; d) L. A. Yakubov, N. E. Galanin, G. P. Shaposhnikov,
N. S. Lebedeva, E. A. Mal’kova, Russ. J. Gen. Chem. 2008, 78, 1255–
1259; e) M. A. Filatov, A. Y. Lebedev, S. A. Vinogradov, A. V. Che-
prakov, J. Org. Chem. 2008, 73, 4175–4185; f) M. A. Filatov, A. V.
Cheprakov, I. P. Beletskaya, Eur. J. Org. Chem. 2007, 3468–3475.
[8] a) N. Noguchi, J. W. Shen, H. Asatani, M. Matsuoka, Cryst. Growth
Des. 2010, 10, 1848–1853; b) M. Xu, A. Ohno, S. Aramaki, K. Kudo,
M. Nakamura, Org. Electron. 2008, 9, 439–444; c) S. V. Apreleva,
D. F. Wilson, S. A. Vinogradov, Appl. Opt. 2006, 45, 8547–8559;
d) O. S. Finikova, T. Troxler, A. Senes, W. F. DeGrado, R. M. Hoch-
strasser, S. A. Vinogradov, J. Phys. Chem. A 2007, 111, 6977–6990;
e) D. F. Wilson, W. M. F. Lee, S. Makonnen, O. Finikova, S. Aprele-
va, S. A. Vinogradov, J. Appl. Physiol. 2005, 101, 1648–1656; f) V.
Gottumukkala, O. Ongayi, D. G. Baker, L. G. Lomax, M. G. H.
Vicente, Bioorg. Med. Chem. 2006, 14, 1871–1879; g) O. Ongayi, V.
Gottumukkala, F. R. Fronczek, M. G. H. Vicente, Bioorg. Med.
Chem. Lett. 2005, 15, 1665–1668.
[20] Y. Matsuzawa, K. Ichimura, K Kudo, Inorg. Chim. Acta 1998, 277,
151–156.
[21] N. Kobayashi, Phthalocyanines: Properties and Applications, Vol. 2,
(Eds.: C. C. Leznoff, A. B. P. Lever), VCH, Weinheim, 1992, p 97.
[22] C. Piechocki, J. Simon, A. Skoulios, D. Guillon, P. Weber, J. Am.
Chem. Soc. 1982, 104, 5245–5247.
[23] a) M. J. Cook, M. F. Daniel, K. J. Harrison, N. B. McKeown, A. J.
Thomson, J. Chem. Soc. Chem. Commun. 1987, 1086–1088; b) A. S.
Cherodian, A. N. Davies, R. M. Richardson, M. J. Cook, N. B.
McKeown, A. J. Thomson, J. Feijoo, G. Ungar, K. J. Harrison, Mol.
Cryst. Liq. Cryst. 1991, 196, 103–114.
[24] a) M. J. Cook, S. J. Cracknell, K. J. Harrison, J. Mater. Chem. 1991,
1, 703–704; b) A. N. Cammidge, M. J. Cook, K. J. Harrison, N. B.
McKeown, J. Chem. Soc. Perkin Trans. 1 1991, 3051–3058; c) A. N.
Cammidge, M. J. Cook, S. D. Haslam, R. M. Richardson, K. J. Harri-
son, Liq. Cryst. 1993, 14, 1847–1862; d) I. Chambrier, M. J. Cook,
S. J. Cracknell, J. McMurdo, J. Mater. Chem. 1993, 3, 841–849.
[25] I. Chambrier, M. J. Cook, M. Helliwell, A. K. Powell, J. Chem. Soc.
Chem. Commun. 1992, 444–445.
[26] Programs CrysAlisPro, Oxford Diffraction Ltd., Abingdon, 2010.
[27] SHELX-97, Programs for crystal structure determination
(SHELXS) and refinement (SHELXL): G. M. Sheldrick, Acta Crys-
tallogr. Sect. A 2008, 64, 112–122.
[9] a) C. E. Dent, J. Chem. Soc. 1938, 1–6; b) J. H. Helberger, Justus
Liebigs Ann. Chem. 1937, 529, 205–218.
[10] a) P. A. Barrett, R. P. Linstead, G. A. P. Tuey, J. M. Robertson, J.
Chem. Soc. 1939, 1809–1820; b) P. A. Barrett, R. P. Linstead, F. G.
Rundall, G. A. P. Tuey, J. Chem. Soc. 1940, 1079–1092.
[11] L. A. Yakubov, N. E. Galanin, G. P. Shaposhnikov, Russ. J. Org.
Chem. 2008, 44, 755–760.
[28] N. B. McKeown, I. Chambrier, M. J. Cook, J. Chem. Soc. Perkin
Trans. 1 1990, 1169–1177.
[29] I. Chambrier, G. F. White, M. J. Cook, Chem. Eur. J. 2007, 13, 7608–
7618.
[12] a) Y.-H. Tse, A. Goel, M. Hu, A. B. P. Lever, C. C. Leznoff, J. E.
Van Lier, Can. J. Chem. 1993, 71, 742–753; b) N. E. Galanin, E. V.
Kudrik, G. P. Shaposhnikov, Russ. J. Gen. Chem. 2004, 74, 282–285.
Received: July 29, 2010
Revised: September 13, 2010
Published online: February 14, 2011
3146
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3136 – 3146