A simple synthesis of symmetric phthalocyanines and their respective perfluoro and transition-metal complexes

Article abstract of DOI:10.1002/aoc.4872

We report a simple synthesis protocol for making phthalocyanines (Pcs) starting from phthalonitriles. This method is general and requires no specialised equipment. The complexes are isolated and characterised using X-ray diffraction, NMR, FTIR and Raman spectroscopy and high-resolution mass spectrometry. First, we study and present a one-step synthesis route to a metal-free Pc (H₂PcH₁₆), as well as to the corresponding MPcH₁₆ complexes of Mn, Fe, Co, Ni, Cu and Zn. Then, we show that this route can also be used to make the fluorinated Pc analogues (MPcF₁₆). Finally, we present a new and useful procedure for inserting a metal ion into a metal-free H₂PcH₁₆ ring, by direct metalation, yielding the corresponding MPcH₁₆ complex. This last method is especially useful if you want to make different MPcH₁₆ complexes.

Full text of DOI:10.1002/aoc.4872

Received: 25 November 2018
DOI: 10.1002/aoc.4872
Revised: 19 January 2019
Accepted: 28 January 2019
F U L L P A P E R
A simple synthesis of symmetric phthalocyanines and their
respective perfluoro and transition‐metal complexes
Ilse M. Denekamp
| Florentine L.P. Veenstra
| Peter Jungbacker
| Gadi Rothenberg
Van't Hoff Institute for Molecular
Sciences, University of Amsterdam,
Science Park 904, Amsterdam 1098 XH,
The Netherlands
We report a simple synthesis protocol for making phthalocyanines (Pcs)
starting from phthalonitriles. This method is general and requires no
specialised equipment. The complexes are isolated and characterised using
X‐ray diffraction, NMR, FTIR and Raman spectroscopy and high‐resolution
mass spectrometry. First, we study and present a one‐step synthesis route to
a metal‐free Pc (H2PcH16), as well as to the corresponding MPcH16 complexes
of Mn, Fe, Co, Ni, Cu and Zn. Then, we show that this route can also be used to
make the fluorinated Pc analogues (MPcF16). Finally, we present a new and
useful procedure for inserting a metal ion into a metal‐free H2PcH16 ring, by
direct metalation, yielding the corresponding MPcH16 complex. This last
method is especially useful if you want to make different MPcH16 complexes.
Correspondence
Gadi Rothenberg, Van't Hoff Institute for
Molecular Sciences, University of
Amsterdam, Science Park 904,
Amsterdam 1098 XH, The Netherlands.
Email: g.rothenberg@uva.nl
KEYWORDS
macrocycles, metalation, NMR, one step synthesis, sustainable chemistry
1 | INTRODUCTION
As part of our ongoing research into selective oxida-
tion with molecular oxygen,[4–6] we tried building syn-
Nature excels at evolving complex catalytic systems that can
carry out “simple” chemical reactions cleanly and efficiently.
The best (and to us chemists, most frustrating) examples are
the enzymes nitrogenase[1] and methane monooxygenase,[2]
which can fix nitrogen from the air and oxidise methane to
methanol under ambient conditions, respectively. Another
example is the activation of dioxygen, which is particularly
challenging owing to its resonance stabilisation.[3] Here,
one of nature's tools is the heme porphyrin molecule, which
is embedded in vivo within the protective shell of the
haemoglobin protein. This combined system shows many
features of an ideal catalyst, operating efficiently at ambient
temperature and pressure and using only a single iron atom
per site. However, transferring this activity to in vitro and
ultimately to industrial setups is far from trivial.
thetic porphyrin analogues that could serve as good
single‐atom catalysts in vitro. For this, we turned to
phthalocyanines (Pcs), which are highly stable two‐
dimensional macrocycles with a structure analogous to
that of porphyrins (Scheme 1). Pcs are by no means
new compounds. They were first characterized in 1934
by Linstead, after their discovery at Scottish Dyes Ltd.,
in Grangemouth.[7] Today, Pcs have a broad range of
applications due to their strong colour and long‐term sta-
bility. The copper phthalocyanine pigment is the single
largest‐volume colorant sold worldwide (mainly thanks
to its availability and low price).[8,9] Pcs are applied as col-
our pigments for cars, due to their strong blue colour,
insolubility in water, high dispersability and high heat
stability.[10,11] They are also found in printing inks,[12]
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© 2019 The Authors Applied Organometallic Chemistry Published by John Wiley & Sons, Ltd.
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DENEKAMP ET AL.
the solvation of various MPcs thanks to its higher boiling
point. The reaction can be monitored visually, as dissolv-
ing the phthalonitrile in n‐pentanol gives a milky liquid,
which turns orange on addition of DBU. When this mix-
ture is heated, it turns a dark blue‐purple, indicating the
formation of the Pc ring, which can then be washed and
isolated (see experimental section for details).
SCHEME 1 left: Heme B, within the porphyrin highlighted in
gray. Right: FePcH16
We then turned to the metal‐Pc complexes, or MPcH16.
In principle, these complexes can be made in two ways.
One can either synthesise them in a single step from the
metal precursor and phthalonitrile, or one can first syn-
thesise H2PcH16 ligand, and then complex it with the
metal salt precursor. The first method is most commonly
used, and here we present only a simplified variation. To
the best of our knowledge, the second method is new.
The direct route to MPcH16 is very similar to the synthesis
of the H2PcH16 ring. The reaction should be run under an
inert atmosphere, not only to prevent the hydrolysis of the
nitrile groups, but also to avoid unwanted oxidation of the
metal cation (manganese, for example, will only form the
complex as Mn2+).[31] The choice of solvent is critical,
because the reaction is run under reflux. Low‐boiling point
solvents such as pentane, cyclohexane, and even n‐butanol
gave only trace amounts of product. Control experiments
showed that n‐pentanol, which boils at 138 °C, gave the
highest yields, with quantitative conversion of the
phthalonitrile precursor after 2 hr.
pen inks,[13,14] general dye applications, biomedical appli-
cations and in catalysis.[15–19]
Pcs can be made by the cyclisation of phthalonitriles in
the presence of an organic base.[18,20–22] However, all
these procedures include cumbersome and/or difficult
synthesis or separation steps. The reactions require high
temperature, typically above 180 °C,[23–25] leading to side
products and lowering yields.[26] Other protocols require
high pressure,[27] ionic liquids,[28] gaseous ammonia[26]
or long reaction times (>150 hr).[29]
Notwithstanding the synthetic achievements of the
above reports, one would prefer a simple, short and gen-
eral synthesis protocol that requires no specialised equip-
ment. In this paper, we present a one‐step synthetic route
to metal‐free Pcs (hereafter noted as H2PcH16), their cor-
responding Mn, Fe, Co, Ni, Cu and Zn complexes
(MPcH16), and the perfluorinated analogues (MPcF16).
Furthermore, we present a new and facile procedure for
making the same complexes by metalation of a metal‐free
H2PcH16 ring.
We first optimised this protocol for CuPcH16, and then
applied it to the synthesis of the manganese, iron, cobalt,
nickel and zinc analogues. All six complexes were
characterised by IR, Raman, XRD and high‐resolution
MS (see experimental section and supporting information
for details).
2 | RESULTS AND DISCUSSION
First, we tried synthesising the metal‐free H2PcH16 ring
following the procedures of Ogawa,[22] Wöhrle[30] and
Kharisov.[21] These protocols give a good basis, advising
the use of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as
the base and alcohol solvents. They are based on the
cyclisation of phthalonitrile (Scheme 2) but should be
done under inert atmosphere, as moisture from the air
can hydrolyse the nitrile groups, forming unwanted side
products. The reaction proceeds best in an alcohol
solvent, and is quite solvent‐dependent.[22] We found that
n‐pentanol is the optimal choice because it also enables
The FTIR spectra of H2PcH16, CuPcH16 and MnPcH16,
Figure 1, show distinctive peaks. Small shifts between the
Pcs are expected due to the different metals. The peak at
SCHEME 2 Cyclisation of phthalonitrile gives the symmetric
FIGURE 1 FTIR spectra of H2PcH16 (black), CuPcH16 (red) and
phthalocyanine
MnPcH16 (blue)

DENEKAMP ET AL.
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ca. 428 cm−1 shows the in‐plane C–C–H bend, while that
at ca. 717 cm−1 pertains to the out‐of‐plane C–C–H bend.
Further, we observe the N–H bend at 752 cm−1, the C–N
stretch at 1118 cm−1, the C–H bend (or possibly C–N
stretch) at 1164 cm−1, a strong C–C stretch peak at
1333 cm−1, and the C=N stretch at 1508 cm−1 [32–34]
.
SCHEME 3 Complexation of the "empty" Pc with various metals;
1
The structure of ZnPcH16 was also confirmed by H‐
NMR, shown in Figure 2. The NMR clearly shows the for-
mation of the highly symmetric complex, with only two
types of chemically different hydrogen atoms, noted in
the figure as α and β. The two double doublets at
δH = 9.46–9.43 and at δH = 8.15–8.12 have coupling con-
stants of 3.0 and 5.6 Hz, respectively, indicating meta and
ortho coupling. This is in good agreement with what is
expected for aromatic systems.[36]
M = Mn, Fe, Co, Cu, Zn
interactions. At the end of the reaction, any excess base
is easily removed by washing with dilute HCl.
The metalation was confirmed by powder X‐Ray dif-
fraction studies, which show a clear difference between
the metal‐free H2PcH16 and the metalated MPcH16.
Figure 3 shows the diffraction patterns for three samples:
an H2PcH16 (black), a CuPcH16 made using the direct
route (red) and a CuPcH16 made by the two‐step method
(blue). The H2PcH16 sample shows four peaks in the
region 2θ = 10–20°, namely at 13.6°, 14.95°, 15.95° and
16.8°. Conversely, both of the CuPcH16 samples show
peaks at 10.65°, 12.6°, 14.2°, 18.25° and 18.65°, which
The second route to MPcH16 involves the insertion of a
metal ion into a metal‐free H2PcH16 ring, giving the
MPcH16 product plus two equivalents of protons
(Scheme 3). This is a new procedure, which we feel has
merit, especially if you want to make several different
MPcH16 complexes. The main barrier to this reaction is
the general insolubility of H2PcH16 (it does dissolve in
methylnaphthalene, even at room temperature, but
unfortunately the metalation does not occur). However,
we found that H2PcH16 dissolves slightly under reflux in
n‐pentanol, giving an opportunity for the metal insertion
to proceed. Once this starts, the reaction runs readily.
Quantitative yield is reached after 2 h, and the product
isolation is simple and straightforward (see experimental
section for details). This reaction doesn't require inert
atmosphere (control experiments showed that the
metalation of CuPcH16 proceeds readily under air).
This metalation requires an organic base to remove the
acidic protons from the centre of the Pc ring. The reaction
proceeds well with either tributylamine (TBA) or
butyldimethylamine (BDMA), but no conversion was
observed in the presence of DBU. We hypothesise that
the 3D bulkiness of TBA and BDMA helps in unstacking
the Pc rings, which are bound to each other by π–π
FIGURE 3 Powder x‐ray diffraction spectrum of H2PcH16
(black), CuPcH16 (red) prepared via the direct route and CuPcH16
(blue) made in the two‐step method. The inset shows the zoomed‐in
spectra for the region 2θ = 10–20°
FIGURE 2 1H‐NMR of ZnPcH16
(300 MHz, CDCl3). The α and β
designations correspond to the two types
of chemically different hydrogen atoms.
Chemical shifts are reported relative to
[35]
CDCl3

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DENEKAMP ET AL.
are distinct from those of H2PcH16. This also confirms
that both metalation protocols result in the same MPcH16
product.
on the top part of the flask, effectively separating your
reagents from each other.
Powder X‐Ray diffraction studies of the different
MPcF16 compounds show one main single peak
(Figure 4), which shifts slightly depending on the metal
ion. In general, complexes of heavier metals show this
peak at higher 2θ values: {MnPcF16, 26.90°}; {FePcF16,
27.65°}; {CoPcF16, 27.70°}; {CuPcF16, 28.45°}; and
{ZnPcF16, 28.6°}.
The first route, starting from the phthalonitrile, can also
be used for making the perfluorinated metal‐Pc complexes
MPcF16 (Scheme 4). These are interesting because the
perfluorinated ring creates a ‘protective shell’ around the
complex that can prevent its oxidation and degradation.
As an added bonus, the perfluorinated metal‐Pc complexes
are much more readily soluble in several organic solvents.
Here we combined two different procedures, from van Lier
et al.[37] and Morley and co‐workers.[38]
3 | CONCLUSIONS
Using 2,3,4,5‐tetrafluorophthalonitrile as our starting
material, we ran the reactions at higher temperatures, typ-
ically 200 °C for CuPcF16 and 250 °C for CoPcF16, ZnPcF16,
FePcF16 and MnPcF16, without any solvent (the reagent
itself melts at ca. 85 °C, so in practice it serves as its own
solvent). The synthesis is straightforward, giving the crude
MPcF16 complexes as dark blue/black solids. After
crushing the hard black solids, any leftover metal salt is
washed away with water. The product is then Soxhlet
extracted using acetone and checked in NMR for starting
material. Note that the type and the size of the reaction ves-
sel is important here, because if you use a too‐large round‐
bottomed flask the tetrafluorophthalonitrile will sublime
We successfully developed the synthesis of H2PcH16,
MPcH16 and MPcF16, for a variety of metals. Furthermore,
we succeeded in inserting a metal into the H2PcH16 struc-
ture. The synthetic protocols are easy, general and can be
performed with standard lab equipment. We trust and
hope that these simple and effective routes will help
researchers who are interested in making phthalocya-
nines, increasing their variety of applications even further.
4 | EXPERIMENTAL SECTION
4.1 | Materials and instrumentation
All chemicals were purchased from either VWR
chemicals, Fluorochem or Merck and were used without
further purification, except for solvents, which were dried
prior to reaction over 3 Å molecular sieves. All experi-
ments were performed under nitrogen atmosphere,
unless stated otherwise.
NMR spectra [1H, 19F] were measured on a Bruker AV
300 spectrometer. IR spectra (4000–400 cm−1, resol.
0.5 cm−1) were recorded on a Varian 660 FTIR spectrom-
eter using ATR and the transmission technique. X‐Ray
diffraction (XRD) patterns were obtained with a MiniFlex
II diffractometer using Ni‐filtered CuKα radiation. The X‐
ray tube was operated at 30 kV and 15 mA, with a 0.01°
step and 1 s dwell time. Raman spectra were recorded
using a Renishaw InVia system (532 and 632.8 nm) and
a Kaiser Optical Systems RXN‐4 system (785 nm) coupled
with fibre optics to an immersion probe with a short focal
length.
SCHEME
Fe(OAc)2, CuCl2, Zn(OAc)2·2H2O
4
MX2
=
Co(OAc)2·4H2O, Mn (OAc)2·4H2O,
Mass spectra were collected on two instruments: (A)
AccuTOF LC, JMS‐T100LP Mass spectrometer (JEOL,
Akishima, Tokyo, Japan). ESI source, positive‐ion mode;
needle voltage 2500 V, orifice 1 voltage 120 V, orifice 2
voltage 9 V; ring Lens voltage 22 V; orifice 1 80 °C,
desolvating chamber 250 °C. The samples were measured
using flow injection with a flow rate of 0.01 ml/min, and
the spectra were recorded with an average duration of
0.5 min. (B) AccuTOF GC v 4 g, JMS‐T100GCV Mass
FIGURE 4 Powder x‐ray diffraction of MPcF16 complexes. The
data for the iron and manganese complexes are omitted for clarity

DENEKAMP ET AL.
5 of 7
spectrometer (JEOL, Japan). FD emitter, Carbotec or
Linden (Essen, Germany), FD 13 μm. Current rate
51.2 mA/min over 1.2 min.
ambient temperature, filtered under vacuum and
washed with water (5 x 10 ml) and then with EtOH (5 x
10 ml). This gave a green powder, weighing 263 mg
(45 mol% based on phthalonitrile). HRMS (FD+) m/z
calc. C32H16N8Zn, 576.078, found 576.085. 1H‐NMR
(300 MHz, CDCl3) δ 9.46–9.43 (8H, double doublet),
8.15–8.12 (8H, double doublet). FTIR (cm−1):1594, 1482,
1328, 1112, 1083, 1058, 885, 746, 728; Raman
shift/cm−1: 160, 591, 674, 1330, 1495.
4.2 | Procedure for synthesising the
metal‐free phthalocyanine (H2PcH16)
Phthalonitrile (0.50 g, 3.9 mmol) was dissolved in n‐
pentanol (2 ml). Then 1,8‐diazabicyclo(5.4.0)undec‐7‐ene
(0.1 ml, 0.7 mmol, DBU) was added and the mixture
was heated for 2 hr at 140 °C, forming a dark
blue/purple solution (adding more DBU is unadvisable
as this creates problems in the workup). The reaction
was cooled down to ambient temperature, filtered and
washed first with water (5 × 10 ml) and then with EtOH
(5 × 10 ml) and dried in air at 20 °C. This yielded the
product as dark blue/purple small needles, 0.33 gram
(66 mol% based on phthalonitrile). HRMS (FD+) m/z cal-
culated C32H18N8, 514.165, found, 514.167. FTIR (cm−1):
1110, 1095, 995, 717; Raman shift/cm−1: 682, 723, 795,
1141, 1337, 1541. XRD (2θ°): 13.6, 14.95, 15.95, 16.8.
The syntheses of FePcH16, MnPcH16, CoPcH16 and
NiPcH16 was similarly performed, using: FeCl2·4H2O
(199 mg, 1 mmol, 16 mol% based on phthalonitrile),
MnCl2·2H2O, (162 mg, 1 mmol, 73 mol%), CoCl2·6H2O
(238 mg, 1 mmol, 21 mol%), Ni(OTf)2 (357 mg, 1 mmol,
66 mol%).
4.4 | Procedure for metalation of the
H2PcH16 (the two‐step method)
The H2PcH16 and the metal salt (1:2.5 equiv) were dis-
solved in n‐pentanol. Tributylamine (TBA) was added
and the mixture was heated for 2 hr at 160 °C and then
cooled down to ambient temperature. The dark coloured
mixture was filtered under ambient pressure, giving a
dark‐coloured cake. This was washed first with water (2
x 10 ml), then with 0.6 M HCl (1 x 10 ml), again with
water (1 x 10 ml) and finally with EtOH (3 x 10 ml).
The dark powder was dried in open air.
4.3 | General procedure for synthesising
metal‐containing phthalocyanines
(MPcH16) via the direct route
Phthalonitrile and the corresponding metal salt were dis-
solved in n‐pentanol after which the DBU was added.
The mixture was heated for 2 hr at 140 °C, forming a
dark coloured solution. The reaction mixture was cooled
down to ambient temperature, forming a solid. This was
filtered under vacuum and washed with water
(5 × 10 ml) and then with EtOH (5 × 10 ml). The residue
was dried under air.
Example 1: CuPcH16: The H2PcH16 (20 mg,
0.04 mmol) and Cu(OAc)2·H2O (20 mg, 0.1 mmol) were
dissolved in n‐pentanol (3.0 ml) together with the TBA
(0.05 ml, 2 mmol). The mixture was heated for 2 hr at
160 °C, forming a dark blue solution. This was allowed
to cool down to ambient temperature and then filtered,
giving a dark‐blue cake. The cake was washed first with
water (2 x 10 ml), then with 0.6 M HCl (1 x 10 ml), again
with water (1 x 10 ml) and finally with EtOH (3 x 10 ml).
The resulting blue powder was dried in air, yielding
40 mg (100 mol% based on the H2PcH16). XRD (2θ°):
10.65, 12.6, 14.15, 18.25, 18.62, 23.8, 26.2.
Example 2: MnPcH16: The H2PcH16 (15 mg,
0.03 mmol) and Mn(OAc)2·4H2O (25 mg, 0.1 mmol) were
dissolved in n‐pentanol (3.0 ml) after which the TBA
(0.05 ml, 2 mmol) was added. The reaction was heated
at 160 °C for 2 hr, forming a green solution. The mixture
was cooled down to ambient temperature and then fil-
tered, giving a dark green cake. The cake was washed first
with water (2 x 10 ml), then with 0.6 M HCl (1 x 10 ml),
again with water (1 x 10 ml) and finally with EtOH (3 x
10 ml). While washing, the product lost its green colour,
turning into a dark blue powder, which was air dried.
Example 1: CuPcH16: Phthalonitrile (0.50 g,
3.9 mmol) and Cu(OTf)2 (362 mg, 1.0 mmol) were dis-
solved in n‐pentanol (2 ml). DBU (0.1 ml, 0.7 mmol)
was added and the mixture was heated at 140 °C for
2 hr, forming a dark blue solution. The reaction was
cooled down to ambient temperature, filtered under vac-
uum and washed with water (5 × 10 ml) and then with
EtOH (5 × 10 ml). This gave the CuPcH16 as a blue pow-
der, 0.40 gram (70 mol% based on phthalonitrile). HRMS
(FD+) m/z calculated C32H16CuN8, 575.079, found,
575.107. FTIR (cm−1): 1612, 1508, 1334, 1118, 1095, 717;
Raman shift/cm−1: 592, 680, 1142, 1340, 1449, 1523.
Example 2: ZnPcH16: Phthalonitrile (0.50 g,
3.9 mmol) and ZnCl2 (136 mg, 1.0 mmol) were dissolved
in n‐pentanol (2 ml). DBU (0.1 ml, 0.7 mmol) was added
and the mixture was heated for 2 hr at 140 °C, forming a
dark green solution. The reaction was cooled down to

6 of 7
DENEKAMP ET AL.
This gave 12 mg (70 mol% based on the H2PcH16). XRD
ACKNOWLEDGEMENTS
(2θ°): 14.1, 15.5, 18.2, 23.75, 26.2.
We thank E. Zuidinga for help with the HRMS measure-
ments. I.M.D. is supported by the NWO TOP‐PUNT pro-
ject Catalysis in Confined Spaces. This work is part of
the Research Priority Area Sustainable Chemistry of the
UvA, http://suschem.uva.nl.
The syntheses of FePcH16, ZnPcH16 and CoPcH16 were
performed similarly, starting from Fe(OAc)2 (17 mg,
0.1 mmol, 100 mol% yield based on the H2PcH16),
Zn(OAc)2·2H2O (26 mg, 0.12 mmol) and Co(OAc)2·4H2O
(20 mg, 0.1 mmol, 57 mol% yield based on the H2PcH16).
ORCID
Ilse M. Denekamp https://orcid.org/0000-0003-2297-4730
Florentine L.P. Veenstra https://orcid.org/0000-0002-7355-
8166
Peter Jungbacker https://orcid.org/0000-0003-3467-0937
Gadi Rothenberg https://orcid.org/0000-0003-1286-4474
4.5 | General procedure for the synthesis
of metal‐containing fluorophthalocyanine
(MPcF16)
Tetrafluorophthalonitrile and the corresponding metal
salt were mixed and heated at 250 °C (200 °C in the case
of copper) for 3 hr in a closed 10 ml round bottom flask.
The reaction mixture was cooled down to ambient tem-
perature, forming a black solid. This was crushed, filtered
and washed with water (5 × 10 ml) and extracted by
soxhlet using acetone. The acetone filtrate was collected
and evaporated, yielding the product.
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SUPPORTING INFORMATION
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How to cite this article: Denekamp IM, Veenstra
FLP, Jungbacker P, Rothenberg G. A simple
synthesis of symmetric phthalocyanines and their
respective perfluoro and transition‐metal
complexes. Appl Organometal Chem. 2019;e4872.
https://doi.org/10.1002/aoc.4872
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