Synthesis and properties of a trinuclear copper(II) complex of a ligand with phthalocyanine and Schiff-base coordination sites

Article abstract of DOI:10.1142/S108842461850013X

A trinuclear copper(II) phthalocyanine complex was synthesized by chelate coordination of the peripherally introduced Schiff-base nitrogen and phenoxide oxygen on the Cu(pc) core to a copper(II) ion. The magnetic, spectral and electrochemical properties w

Full text of DOI:10.1142/S108842461850013X

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2018; 22: 1–7
DOI: 10.1142/S108842461850013X
Published at http://www.worldscinet.com/jpp/
Synthesis and properties of a trinuclear copper(II)
complex of a ligand with phthalocyanine and Schiff-base
coordination sites
Makoto Handaa,*◊, Kenichi Kanagawaa, NatsumiYanoa, HarukiYairia,
Airi Okunoa, Minoru Mitsumib andYusuke Kataokaa
aDepartment of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University,
1060 Nishikawatsu, Matsue 690-8504, Japan
bDepartment of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Kita-ku,
Okayama 700-0005, Japan
Dedicated to Professor Kazuchika Ohta on the occasion of his retirement
Received 29 November 2017
Accepted 5 January 2018
ABSTRACT: A trinuclear copper(II) phthalocyanine complex was synthesized by chelate coordination
of the peripherally introduced Schiff-base nitrogen and phenoxide oxygen on the Cu(pc) core to a
copper(II) ion. The magnetic, spectral and electrochemical properties were compared with those of the
precursor mononuclear Cu(pc) complex with the NO chelate coordination site and a mononuclear Schiff-
base copper(II) complex corresponding to the central bis-chelated unit of the title trinuclear complex. A
stronger aggregating nature of the trinuclear complex compared with the precursor mononuclear Cu(pc)
complex was confirmed by the spectral change of the Q band feature coming from the coordination to
the copper(II) ion in dichloromethane. Two successive pc-ring reduction waves were not observed for the
trinuclear complex in dichloromethane containing TBP(PF6), alternatively showing an irreversible wave
in the reduction side. The central bis-chelated copper(II) ion was considered to play an important role for
the redox behavior of the trinuclear complex.
KEYWORDS: trinuclear copper(II) phthalocyanine, peripheral Schiff-base coordination site, spectral
properties, magnetic properties, electrochemical properties.
as nonlinear optics (NLO), optical storage devices,
chemical sensors, electrochromic devices, photo-
INTRODUCTION
Much interest has been devoted to phthalocyanines
sensitizers in photodynamic therapy (PDT), etc. [5–9].
and their metal complexes ([M(pc)]) for their unique
Schiff-base complexes have attracted many chemists for
properties based on the extended p-system within the
their interesting electrochemical, catalytic and magnetic
ligands [1–4]. The strong absorption in the near-infrared
properties [10–19]. If metallophthalocyanine ([Mpc])
region (650–700 nm) observed for them, called the
and Schiff-base complexes are combined within a
Q band, is the reason why they show remarkable blue
molecule, new interesting properties could be produced
or green colors, leading to their longtime use as dyes
by the combination. Based on such a concept, we have
and pigments. Recently, they have been also applied
been engaged in synthesizing pc-Schiff-base conjugated
complexes and reported dinuclear complexes ([M1–
◊ SPP full member in good standing.
M2(La)], M1 = NiII, CuII; M2 = NiII, CuII, VIVO) [20, 21]
and tetranuclear complexes ([Cu4(Lb)Cl2(m-OH)]) [22],
structures of which are shown in Scheme 1. In this
study, we synthesized a trinuclear copper(II) complex
*Correspondence to: Makoto Handa, email: handam@riko.
shimane-u.ac.jp, tel.: +81-852-32-6418, fax: +81 852-32-
6429.
Copyright © 2018 World Scientific Publishing Company

2
M. HANDA ET AL.
(a)
R
R
RESULTS AND DISCUSSION
The synthetic procedure from [Cu{pc(t-
Bu)3(NH2)}] to the title trinuclear complex
[{Cu(L1)}2Cu] (2) through the mononuclear
complex [Cu(HL1)] (1) is illustrated in
Scheme 3. The peripheral amino group on the
pc ring of [Cu{pc(t-Bu)3(NH2)}] reacts with
carbonyl group of salicylaldehyde to give the
coordinating site consisting of Schiff-base
nitrogen (N) and phenoxide oxygen (O) atoms.
The NO chelate coordination to copper(II) ion
produced the trinuclear complex. In order to
investigatetheNOchelatecoordinatedcopper(II)
site, a mononuclear complex [Cu(L2)2] (3) was
prepared and its crystal structure determined.
The crystal structure is drawn in Fig. 1.
Selected bond distances and angles are given
in Table S1 (see Supporting information). The
crystallographical inversion center exists at the
central copper atom of the mononuclear unit,
hence giving the bond angles of O1–Cu1–O1′ =
180° and N1–Cu1–N1′ = 180°. The coordination
geometry around the copper(II) ion adopts a
square planar geometry, and two NO chelate
ligands (L2) coordinate to the copper(II) ion with
the trans arrangement. The Cu–O and Cu–N
bond distances are 1.886 (1) and 2.015 (2) Å,
respectively, which are comparable to those
for the copper(II) complexes with the NO type
Schiff-base ligands derived from condensation
of aniline and salicylaldehyde derivatives
[23–36]. It seems to be usual that N2O2-tetra-
coordinated copper(II) complexes with Schiff-
base ligands adopt trans square planar, distorted
square planar or tetrahedral geometry. However,
a cis arrangement of the copper(II) complex
with the same ligand as the present study (L2)-
has been reported for [Cu(L2)]•DMF [31]. In
[Cu(L2)]•DMF, the copper(II) ion has a distorted
square planar structure with a dihedral angle
of 40.5(1)° between two CuNO coordination
planes, where Cu–N = 1.965 (3) Å and Cu–O =
1.903(2)and1.895(2)Å. DMFexistsasacrystal
solvent in the crystal, showing intermolecular hydrogen
bonds with the Cu-complex unit. Although there have
been discussions on the trans–cis isomerism concerning
the copper(II)-Schiff-base complexes obtained by NO
bidentate coordination, to our knowledge, the ligand HL2
is the first example to give both cis and trans isomers
structurally determined by X-ray structure analysis.
Figure 2 shows temperature dependence of molar
magnetic susceptibility (cM) and effective magnetic
moment (meff) for the complex 2. The moment (per a
trinuclear molecule; meff = (8cM•T)1/2) is 3.43 mB at 300 K,
which is rather close to the spin-only value (meff = 3.00 mB)
for magnetically independent three unpaired electrons
N
N
N
N
O
R
R
N M1
N
N
M2
R =
O
N
O
N
N
M1 = NiII, CuII
M2 = NiII, CuII, VIVO
R
R
[M1-M2(La)]
(b)
N
N
N
N
N
N
N
O
N
Cu
Cl
N Cu
N
N
Cu
N Cu
N
N
Cl
O
N
N
N
N
H
[Cu4(Lb)Cl2(µ-OH)]
Scheme 1. Chemical structures of [M1–M2(La)] (a) and [Cu4(Lb)Cl2(m-OH)] (b)
N
N
N
N
N
Cu
N
N
Cu
N
N
O
O
N
N
Cu
N
N
N
N
N
N
N
[{CuL1)}2Cu]
Scheme 2. Chemical structure of [{Cu(L1)}2Cu] (2)
of a fused ligand having phthalocyanine and Schiff-base
coordination sites (H3L1). The chelate coordination of
NO donor atoms of a peripherally introduced Schiff-
base site onto the pc ring of a copper(II) complex
[Cu(HL1)] (1) to a copper(II) ion gave the objective
trinuclear complex [{Cu(L1)}2Cu] (2), the structure of
which is shown in Scheme 2. Further, we prepared a
mononuclear copper(II) complex of a Schiff-base ligand
N-(4-methylphenyl)salicylaldimine (HL2), because the
copper(II) complex [Cu(L2)2] (3) corresponds to the
central part of the trinuclear copper(II) complex 2. Here,
we report on the syntheses and magnetic, spectroscopic,
and electrochemical properties of the complexes 1–3 as
well as the crystal structure of 3.
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 2–7

SYNTHESIS AND PROPERTIES OF A TRINUCLEAR COPPER(II) COMPLEX OF A LIGAND WITH PHTHALOCYANINE
3
NH2
N
N
N
N
N
+
N
Cu
N
N
OH
O
[Cu{pc(t-Bu)3(NH2)}]
EtOH, ∆
Fig.2.Temperaturedependencesofmagneticsusceptibility
and moment of 2
N
OH
N
Cu
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
[Cu2(HL1)]
Cu
N Cu
N
N
N
N
N
Cu(OAc)2•H2O EtOH / dioxane, ∆
[{Cu(L1)}2Cu]
[Cu2{(pc)2(t-Bu)6}]
Scheme 3. Synthetic procedure from [Cu{Pc(t-Bu)3(NH2)}] to
[{Cu(L1)}2Cu] (2)
Scheme 4. Chemical structure of [Cu2{(pc)2(t-Bu)6}]
complex 3 does not show such decrease in the low
temperature region, as shown for Fig. S1 (see Supporting
information). A tetranuclear copper(II) complex [Cu4(Lb)
Cl2(m-OH)] (Scheme 1(b)) was reported to demonstrate
a negligible interaction through an imino nitrogen and a
benzene ring of the pc ligand between CuII(pc) and central
dinuclear CuII units. The entire temperature-dependent
magnetic moment behavior of 2 is similar to a dinuclear
complex [Cu2{(pc)2(t-Bu)6}] (Scheme 4), which did not
display any important interaction through the common
benzene ring, but showed a weak interaction due to
the aggregation nature due to the enlarged p-conjugate
system [37].
Absorption spectra of 1 and 2 measured in dichloro-
methane are displayed in Figs 3 and 4, respectively. Com-
plexes 1 and 2 show the Q band peaks both at 682 and 681
nm, respectively, where the molar extinction coefficient
-1
(e/M-1 cm ) is calculated to be the value per a Cu(pc) unit
.
for 2. It is well-known that the Q band is blue-shifted and
appearsasabroadbandwhenthephthalocyaninemolecules
aggregate in a face to face mode [4, 38].Although complex
1 shows the aggregating nature because the shoulder band
at the shorter wavelength region comes to be remarkable
Fig. 1. ORTEP view of [Cu(L2)2] (3) with 50% probability
displacement ellipsoids. Prime refers to the equivalent position
(-x, -y, -z)
in accordance with the decrease in the Q band intensity
(S = 1/2 for each Cu(II) ion). The moment decreases
slightly with the decrease of temperature to ca. 10 K. The
decreasebecomessteepbelow10K,whichwasconsidered
to originate from an inter- or intra-molecular interaction
between Cu(II) centers. The mononuclear Schiff base
-1
(e /M-1 cm ) when the concentration is increased from
.
2.0 × 10-6 M to 2.5 × 10-5 M, the aggregating nature is
stronger for 2, showing a much weaker Q band intensity
with a stronger shoulder band compared with those of 1.
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 3–7

4
M. HANDA ET AL.
Fig. 3. Absorption spectra of 1, which were measured in
dichloromethane at the concentrations of 2.0 × 10-6 (—), 4.0 ×
10-6 (—), 6.0 × 10-6 (—), 1 × 10-5 (—), 1.25 × 10-5 (—) and
2.5 × 10-5 M (—)
Fig. 6. Cyclic voltammograms of 1, 2 and 3 in
dichloromethane ([complex] = 1 × 10-4 M; [TBA(PF6)] =
-1
.
0.1 M; scan rate = 50 mV s )
A similar phenomenon has been observed for the tetranu
clear complex [Cu4(Lb)Cl2(m-OH)], which showed a
stronger aggregating nature compered with the corres-
ponding dinuclear complex [Cu2(HLb)]. The enlarged
planarity of the complex molecule by the coordination
of the Schiff-base sites to copper(II) ions was considered
to be the plausible reason for the increased aggregating
natures of 2 and [Cu4(Lb)Cl2(m-OH)]. Interestingly, the
Fig. 4. Absorption spectra of 2, which were measured in
dichloromethane at the concentrations of 2.0 × 10-6 (—), 4.0 ×
10-6 (—), 6.0 × 10-6 (—), 1 × 10-5 (—), 1.25 × 10-5 (—) and 2.5 ×
10-5 M (—)
spectral feature of 2 changed in DMF (Fig. 5) (lmax
=
680 nm for the Q band) and became much similar to that
of 1, of which spectrum measured in DMF is given in
Fig. S2 (lmax = 682 nm for the Q band) (see Supporting
information). The geometrical change around the central
copper(II) ion in DMF from dichloromethane may be
related to the observed spectral change.
Figure 6 displays cyclic voltammograms (CVs)
measured in dichloromethane containing TBP(PF6)
(0.1 M) for 1, 2 and 3. There are redox couples (E1/2
=
-0.96 and -1.35 V vs. SCE) on the reduction side for 1,
which can be assigned to reduction at the pc ring because
the copper(II) phthalocyanine with four t-butyl groups
[Cu{pc(t-Bu)4}]showedthecorrespondingredoxcouples,
similarly at E1/2 = -1.42 and -1.78 V vs. Fc+/Fc [22], when
taking E1/2 (Fc+/Fc) = ca. 0.45 V vs. SCE into account
[39]. The broad wave in the oxidation side (ca. 0.7 V vs.
SCE) was attributed to the oxidation of the aggregated pc
rings [40, 41]. The redox behavior is nearly the same as
Fig. 5. Absorption spectra of 2, which were measured in DMF at
the concentrations of 1.0 × 10-6 (—), 1.25 × 10-6 (—), 2.5 × 10-6
(—), 5.0 × 10-6 (—) and 1.0 × 10-5 M (—)
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 4–7

SYNTHESIS AND PROPERTIES OF A TRINUCLEAR COPPER(II) COMPLEX OF A LIGAND WITH PHTHALOCYANINE
5
purchased from Wako Pure Chemical Industries, Ltd. and
used as being supplied.
[Cu(HL1)] (1): [Cu{pc(t-Bu)3(NH2)}] (76 mg, 0.10
mmol) and salicylaldehyde (122 mg, 1.0 mmol) were
dissolved in ethanol (10 mL) and refluxed for 16 h. After
the solvent was removed by evaporation, the resultant
solid was chromatographed on a silica gel column with
a chloroform–toluene (25:1) solvent mixture as an
eluent. The first fraction was collected and evaporated
to remove the solvent. The obtained green powder was
recrystallized using hexane (20 mL), collected again by
the filtration, and dried under vacuum. The yield was
17.2 mg (20% based on [Cu{pc(t-Bu)3(NH2)}] ). Anal.
calcd. for C51H45CuN9O: C, 70.94; H, 5.25; N, 14.60%.
Found C, 70.68; H, 5.27; N, 14.35. HR-MS (ESI-TOF):
m/z 863.3091 (calcd. for [M+H]+ 863.3116).
[{Cu(L1)}2Cu] (2): To an ethanolic solution (60 mL)
of copper(II) acetate was added a solution of 1 (34.6 mg,
0.04 mmol) dissolved in 1,4-dioxane (20 mL). The
solution was refluxed for 3 h and followed by evaporation
to a small portion (ca. 10 mL) and addition of hexane
(20 mL). The green precipitate was collected by suction
filtration, washed with ethanol, and dried under vacuum.
The yield was 33.3 mg (93.8% based on 1). Anal. calcd.
for C102H88Cu3N18O2: C, 68.50; H, 4.96; N, 14.10%.
Fig. 7. Cyclic voltammograms of 1, 2 and 3 in DMF ([complex] =
1 × 10 M; [TBA(PF6)] = 0.1 M; scan rate = 50 mV s )
Found C, 67.88; H, 5.15; N, 13.76. HR-MS (ESI-TOF):
-4
-1
.
m/z 1810.4817 (calcd. for [M+Na]+ 1810.5126).
[Cu(L2)2] (3): p-Toluidine (213 mg, 2mmol) and
salicylaldehyde (244 mg, 2 mmol) were mixed and
refluxed with stirring for 30 min in methanol (40 mL). To
the reaction solution, copper(II) acetate monohydrate
(200 mg, 1 mmol) in methanol (25 mL) was added and
refluxed further for 16 h. The resultant solution was
evaporated to 20 mL and stored in refrigerator (at ca.
0°C) to give a brown precipitate, which was collected by
suction filtration, washed with a small amount of meth-
anol, and dried under vacuum. The yield was 421 mg
(87.0%). Anal. calcd. for C28H24CuN2O2: C, 69.48; H,
5.00; N, 5.79%. Found C, 69.32; H, 4.75; N, 5.85. Single
crystals suitable for X-ray crystal structure analysis were
obtained by recrystallization from methanol.
those observed for [Cu4(Lb)Cl2(m-OH)] and [Cu2(HLb)]
[22]. Complex 2 shows completely different behavior,
with only an irreversible wave being found at ca. -0.95 V
in the reduction side, although the mononuclear Schiff-
base complex 3 shows a reversible or quasi-reversible
wave at E1/2 = -0.75 V vs. SCE. Further, 2 shows the redox
couples at E1/2 = -0.82 and -1.22 V vs. SCE similarly
to 1 (E1/2 = -0.78 and -1.14 V vs. SCE) when the CVs
were measured in DMF containing TBP(PF6) (0.1 M)
(Fig. 7). The different redox behaviors of 2 observed in
dichloromethane and DMF may be related to the fact that
the copper(II) ion adopts different geometrical structures
in dichloromethane and DMF as confirmed by their Q
features in the absorption spectra. Complex 3 shows
an irreversible reduction wave at ca. -0.6 V vs. SCE in
DMF; the redox wave has been previously reported at a
similar potential around -1.0 V vs. Ag/AgCl in DMF for
the same, but cis-isomer complex [31].
Measurements
Elemental analyses for carbon, hydrogen, and nitrogen
were carried out using a Yanako CHN CORDER MT-6.
Absorption spectra were measured in dichloromethane
and DMF using
a JASCO V-670 spectrophoto-
meter. ESI-TOF mass spectra were taken on a Bruker
micrOTOF system. Cyclic voltammograms were taken
in dichloromethane and DMF solutions containing tetra-
n-butylammonium hexafluorophosphate [TBA(PF6)]
on a BAS ALS-DY2325 Electrochemical Analyzer.
A glassy carbon disk (1.5 mm radius), platinum wire,
and saturated calomel electrodes were used as working,
counter, and reference electrodes, respectively. Variable–
temperature magnetic susceptibility measurements were
EXPERIMENTAL
Syntheses of complexes
Copper(II) phthalocyanine with an amino group
and three t-butyl groups ([Cu{pc(t-Bu)3(NH2)}]) was
prepared according to the method described in the
literature [42]. Salicylaldehyde and p-toluidine were
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 5–7

6
M. HANDA ET AL.
Table 1. Crystallographic data and structure refinement of
[Cu(L2)2] (3)
peripherally introduced Schiff-base nitrogen and
phenoxide oxygen on the {Cu(pc)(t-Bu3)} core to a
copper(II) ion. The magnetic and spectral properties
were compared with those of the precursor mononuclear
Cu(pc) complex with the NO chelate coordination
site (1) and the mononuclear Schiff-base copper(II)
complex (3) corresponding to the central bis-chelated
unit of the trinuclear complex. A stronger aggregating
nature of the trinuclear complex compared with the
precursor mononuclear complex was confirmed by the
spectral change of the Q band feature coming from the
coordination to the copper(II) ion in dichloromethane.
Further, two successive pc-ring reduction waves were
not found for the trinuclear complex in dichloromethane
containing TBP(PF6), alternatively showing an
irreversible wave in the reduction side. It was considered
that the central bis-chelated copper(II) ion should play
an important role for the redox behavior. However,
it is still unknown why only the present trinuclear
complex showed the behavior whereas the tetranuclear
copper(II) complex of a pc-Schiff-base fused ligand
with a hydroxide- and phenoxido-copper(II) binuclear
core [Cu4(Lb)Cl2(m-OH)] did not show such a behavior.
The trinuclear complex with a redox inactive metal
ion at the central coordinated unit could give the
useful information. Efforts to prepare the hetero-
metal complexes such as Cu–Zn–Cu and Zn–Zn–Zn
combinations are being made in our laboratory.
Parameter valuesa
Empirical formula
C28H24CuN2O2
Formula mass
484.03
Temperature, T (K)
Crystal system
150
Monoclinic
P21/c
Space group
a (Å)
12.110 (4)
7.327 (2)
13.438 (4)
111.062 (3)
1112.7 (6)
2
b (Å)
c (Å)
b (°)
Unit-cell volume, V (Å3)
Formula per unit cell, Z
Density, Dcalcd (g cm-3)
Crystal size (mm)
Absorption coefficient, m (mm-1)
q range for data collection (°)
Reflections collected/unique
R indices [I > 2s(I)]b
Goodness-of-fit on F2
1.445
0.160 × 0.100 × 0.030
1.010
3.249–25.996
2096/1777
R1 = 0.0300, wR2 = 0.0777
1.073
a Standard deviations in parentheses; b R1 = S||Fo| – |Fc||/S|Fo|;
wR2 = [Sw(Fo2–Fc2)2/S(Fo2)2]1/2.
Acknowledgments
carried out using a superconducting quantum interference
device (SQUID) MPMSXL-5 from Quantum Design.
The measured data were corrected for diamagnetic
contributions [43].
The present work was partially supported by Grants-
in-Aid for Scientific Research Nos. 15K17897 and
16K05722 from the Ministry of Education, Culture,
Sports, Science and Technology (MEXT, Japan). The
authors are grateful to Dr. Michiko Egawa (Shimane
University) for her measurements of elemental analyses
and Prof. Masahiro Mikuriya (Kwansei Gakuin
University) for his helpful discussion.
X-ray diffraction data of complex 3 was collected at 150
K on a RIGAKU Saturn 724 CCD system equipped with
Mo rotating-anode X-ray generator with Monochromated
Mo Ka radiation (l = 0.71075 Å) and were processed
with using CrystalClear-SM 2.0 program (RIGAKU).
The structure of complex 3 was solved by the direct
method (SIR-2011) and refined using the full-matrix
least-squares technique F2 with SHELXL2014 equipped
in the CrystalStructure 4.2.5 software (RIGAKU).
Non-hydrogen atoms were refined with anisotropic
displacement, and almost all of the hydrogen atoms were
located through a difference Fourier map and refined with
isotropic thermal parameters. Crystal data as well as the
details of data collection and refinement for complex 3 are
summarized in Table 1 and can be obtained as a CIF file
from Cambridge Crystallographic Data Center (CCDC).
The deposition number of complex 3 is CCDC-1587713.
Supporting information
Selected bond distance and angles of 3 (Table S1),
temperature dependences of magnetic susceptibility and
moment of 3 (Fig. S1) and absorption spectra of 1 in
DMF (Fig. S2) are given in the supplementary material.
This material is available free of charge via Internet at
http://www.worldscinet.com/jpp/jpp.shtml.
Crystallographic data have been deposited at the
Cambridge Crystallographic Data Centre (CCDC) under
number CCDC-1587713. Copies can be obtained on
request, free of charge, via the internet at http://www.
ccdc.cam.ac.uk/data_request/cif or from the Cambridge
Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44 1223-336-033 or
email: deposit@ccdc.cam.ac.uk).
CONCLUSION
A trinuclear copper(II) phthalocyanine complex (2)
was synthesized by chelate coordination of the
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SYNTHESIS AND PROPERTIES OF A TRINUCLEAR COPPER(II) COMPLEX OF A LIGAND WITH PHTHALOCYANINE
7
23. FernándezJM,Lembrino-CanalesJJandVillena-IR.
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