Synthesis, characterization and spectroscopic studies of novel peripherally tetra-imidazole substituted phthalocyanine and its metal complexes, the computational and experimental studies of the novel phthalonitrile derivative

Article abstract of DOI:10.1016/j.jorganchem.2012.03.016

Compound (3) was synthesized by the reaction of 4-(4,5-diphenyl-1H- imidazol-2-yl) phenol and 4-nitrophthalonitrile in dry DMF in presence of K ₂CO₃ and obtained as single crystal form suitable for x-ray analysis. Vibrational assignm

Full text of DOI:10.1016/j.jorganchem.2012.03.016

Journal of Organometallic Chemistry 713 (2012) 1e10
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis, characterization and spectroscopic studies of novel peripherally
tetra-imidazole substituted phthalocyanine and its metal complexes,
the computational and experimental studies of the novel phthalonitrile derivative
a
a
a
,
b
*
ꢀ
Hakkı Türker Akçay , Rıza Bayrak , Selami Karslioglu , Ertan S¸ ahin
a Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon, Turkey
b Department of Chemistry, Faculty of Arts and Sciences, Atatürk University, 25240 Erzurum, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Compound (3) was synthesized by the reaction of 4-(4,5-diphenyl-1H-imidazol-2-yl) phenol and
4-nitrophthalonitrile in dry DMF in presence of K2CO3 and obtained as single crystal form suitable for
x-ray analysis. Vibrational assignments and electronic transitions of the compound (3) were calculated
and compared with the experimental results. Compound (4) was obtained from compound (33), by
heating at 160 ꢀC for 24 h under N2 atmosphere in dry N,N dimethyl aminoethanol. Compounds (5e8)
were synthesized by the same method applied for the synthesis of compound (4) with addition of the
corresponding metal salts (ZnCH3COO2, NiCl2, CoCl2, CuCl2). Prepared phthalocyanines were purified by
column chromotography using appropriate solvent system and characterized by elemental analysis 1H
NMR, 13C NMR, UVevis, IR and mass spectra. Aggregation behavior of compound (5) was studied in
different solvents and different concentrations in DMSO. In addition, protonation behavior of the
compound (5) was investigated in different mixtures of sulfuric acid and DMSO.
Received 1 February 2012
Received in revised form
9 March 2012
Accepted 13 March 2012
Keywords:
Imidazole
Aggregation in solution
Absorbtion spectrum
Protonation of phthalocyanine
TD-DFT
X-ray analysis
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
The main disadvantage of these valuable materials is their
insolubility in majority of solvents due to intermolecular interac-
Phthalocyanines (Pcs), one of the most useful heterocyclic
materials, can be introduced as tetraazapyrole derivatives.
Although history of the Pcs is about 70 years, there are still many
investigations on their technological applications in different
scientific disciplines. Pcs and their metal complex derivatives,
tions between the macrocycles. The solubility of Pcs can be
increased by various methods such as transforming into cationic
species, axially substitution and perypheral/non-perypheral
substitutions [18e21]. Especially peripherally and non-peripher-
ally substituted phthalocyanines, depending on the structure of the
substituent, are soluble in common organic solvents [22e26]. The
most important advantage of Pcs compared to porphyrines is that
their Q bands are at longer wavelengths and more intense. Thanks
to the special optical properties of phthalocyanines, it’s known that
some phthalocyanines show biological activity against tumors [27].
On the other hand imidazole derivatives consisting of five
membered ring system containing two nitrogen atoms are impor-
tant heterocyclic compounds. These compound classes are used in
many fields such as P38 MAP kinase [28], antivascular disrupting,
antitumor activity [29], ionic liquids [30], anion sensors [31],
electrical and optical materials [32e34]. Imidazole substituted
porphyrines are important structures which are investigated for
their optical, electronic and catalytic properties [35e37]. Addi-
tionally, imidazole substituted phthalocyanines can be used in
different research areas such as phthodynamic therapy [38], elec-
tron transfer processes [39] and synthesis of polymeric phthalo-
cyanines [40].
thanks to properties such as strong delocalized 18
p-electronic
structure, good thermal stability and visible area optical properties,
are used in many technological investigations such as chemical
sensors [1e3], electrochromic displaying systems [4], non-linear
optics [5], solar cells [6], photo-voltaic optics, molecular elec-
tronics [7], semiconductors [8], liquid crystals [9], optical storage
devices [10], laser dyes [11], catalyst [12] and photodynamic
therapy (PDT) [13]. The central cavities of Pc can complex with
about 70 different elements. Depending on specification of
elements; monomeric, axially ligated or dimeric phthalocyanines
can be obtained. The cations fitting the central cavity of phthalo-
cyanines form monomeric species [14], the larger cations form
dimeric or axially ligated species [15e17].
* Corresponding author. Fax: þ90 462 325 3196.
ꢀ
E-mail address: karslis@ktu.edu.tr (S. Karslioglu).
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2012.03.016

2
H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
Synthesis of phthalocyanines containing peripherally
and dietyhl ether respectively, and dried in vacuo. The green
solid product was purified by column chromotography with
chloroform:methanol (100:2) as eluent. Yield: 59 mg (30%),
mp > 300 ꢀC.
substituted imidazole ring is a promising enterprise in terms of
developing new technological materials. In this study, a novel metal
free phthalocyanine and its Zn-, Ni-, Co- and Cu- complexes con-
taining peripherally highly conjugated imidazole substituent were
synthesized. The aggregation behavior of ZnPc at different
concentrations and in different solvents was also investigated. In
addition, crystal structure of the novel phthalonitrile derivative
(compound 3) was explained and comparative investigation of
vibrational and electronic transition features were performed
theoretically and experimentally.
Anal.calc. for C116H74N16O4: C, 79.34; H, 4.25; N, 12.76.
Found: C, 79.41; H, 4.12; N, 12.82.
IR (KBr tablet) ymax/cmꢁ1: 3285, 3049, 1603, 1486, 1469, 1448,
1231, 1166, 1091, 1010, 929, 873, 853, 763.
1H NMR (DMSO-d6) (
d: ppm): 11.19 (bs, 4H, eNH), 8.20e7.85 (m,
20H, AreH), 7.68 (s, 12 H/AreH), 7.60e7.01 (m, 36 H/AreH).
MS (ESI) (m/z): Calculated: 1754.6; Found: 1755.8 [M þ H]þ.
UVevis (DMSO) lmax/nm: [(10ꢁ5 , dm3 molꢁ1 cmꢁ1)]: 698
3
2. Experimental and computational details
(4.72), 664 (4.68), 642 (4.26) 598 (4.01), 342 (4.47).
All reactions were carried out under dryand oxygen free nitrogen
atmosphere using schlenk system. DMF was dried and purified as
described by Perrin and Armarego [41], 4-(4,5-diphenyl-1H-imida-
zol-2-yl) phenol (1) [42] and 4-nitrophthalonitrile (2) [43] were
prepared as described in the literature. 1H NMR/13C NMR spectra
were recorded on a Varian XL-200 NMR spectrometer in CDCl3,
2.1.3. The general procedure for the synthesis
of metallophthalocyanines (5e8)
A mixture of compound (3) (0.2 g, 0.45 mmol), related anhy-
drous metal salts (M ¼ NiCl2 (15.42 mg, 0.12 mmol); CoCl2
(15.6 mg, 0.12 mmol); CuCl2 (16.0 mg, 0.12 mmol)) and
Zn(CH3COO)2 (22.29 mg, 0.12 mmol), dry DMAE (4 ml) and DBU
(3 drops) were mixed in a schlenk tube, then the mixtures were
heated and stirred at 160 ꢀC for 24 h under N2 atmosphere. After
cooling to room temperature, methanol (30 ml) was added, and
then reaction mixtures were refluxed to precipitate the products
which were then filtered off. The green solid products were
washed using hot ethanol, acetone and diethylether respectively,
and dried in vacuo. Purifications of the solid product were
accomplished by column chromatography with silica gel. The
chemical and physical characterizations of the final products 5e8
were given bellow.
DMSO d6, and chemical shifts were reported (d) relative to Me4Si as
internal standard. IR spectra were recorded on a PerkineElmer
Spectrum One FTeIR spectrometer with ATR technique. The MS
and MSeMS spectrawere measured with a Thermo Quantum Access
Mass spectrometer with H-ESI probe. Methanol, chloroform and
acetonitrile were used as solvents in mass analysis and all mass
analysis were conducted in positive ion mode. Elemental analysis
was performed on a Costech ECS 4010 instrument, UVevis spectra
were recorded by Perkin Elmer Lambda 25 spectrometer, using 1 cm
path length cuvettes at room temperature. Melting points were
measured by an electrothermal apparatus. All theoretical calcula-
tions were performed with gaussian 03W software package [44].
2.1.3.1. Synthesis of zinc (II) phthalocyanine (5). Eluent
for column chromatography: chloroform:methanol (100:3).
Yield: 112 mg (55%), mp >300 ꢀC.
2.1. Synthesis of the compounds (3e8)
Anal. Calc. for C116H72N16O4Zn: C, 76.58; H, 3.99; N, 12.32.
Found: C, 77.01; H, 3.87; N, 12.01.
2.1.1. 4-[4-(4,5-diphenyl-1H-imidazol-2-yl)phenoxy]phthalonitrile (3)
4-(4,5-diphenyl-1H-imidazol-2-yl) phenol (1) (1 g, 3.2 mmol)
and 4-nitrophthalonitrile (2) (0.55 g, 3.2 mmol) were dissolved in
dry DMF (10 ml) under N2 atmosphere. After stirring for 10 min at
55 ꢀC, dry finely powdered potassium carbonate (0.48 g, 3.5 mmol)
was added portion wise within 2 h with efficient stirring. The
reaction mixture was stirred under N2 atmosphere at 55 ꢀC for 5
days. Then the reaction mixture was poured into 250 ml ice-water
and precipitate was filtered off, washed with water, diethylether
and dried in vacuo. Residue was crystallized from acetone/ethanol
solvent system., Colorless needle shape crystals, suitable for X-ray
analysis were obtained. Yield 0.9 g (64%), mp: 274 ꢀC.
IR (KBr tablet) ymax/cmꢁ1: 3057, 1603, 1488, 1469, 1450, 1234,
1164, 1093, 1045, 968e945.
1H NMR (DMSO) (
d: ppm): 12.71 (bs, 4H, eNH), 8.86 (bs, 4H,
AreH), 8.74e8.42 (m, 8H/AreH), 8.33 (bs, 8H/AreH), 7.68e7.67
(d 12 H/AreH), 7.53 (m 16 H/AreH), 7.38e7.34 (m, 18H/AreH).
MS (ESI) (m/z): Calculated: 1816.5; Found: 1817.6 [M þ H]þ.
UVevis (DMSO) lmax/nm [(10ꢁ5 , dm3 molꢁ1 cmꢁ1)] : 680
3
(4.92), 612 (4.12), 357 (4,49).
2.1.3.2. Synthesis of Nickel (II) phthalocyanine (6). Eluent
for column chromatography: chloroform:methanol (100:4).
Yield: 91 mg (44%), mp > 300 ꢀC.
Anal.calc. for C29H18N4O: C, 79.44; H, 4.14; N, 12.78.
Found: C, 79.32; H, 4.20; N, 12.84.
Anal.calc. for C116H74N16O4: C, 76.86; H, 4.00; N, 12.36.
Found: C, 76.75; H, 4.09; N, 12.38.
1H NMR (DMSO-d6) (
d:ppm): 12.75 (s,1H, eNH), 8.19e8.15 (d, 2H,
AreH), 8.10 (s, 1H/AreH), 7.88 (s, 1H/AreH), 7.48e7.40 (m,
11H/AreH), 7.32e7.27 (d, 2H/AreH).
IR (KBr tablet) ymax/cmꢁ1: 3057, 1604, 1488, 1470, 1413, 1236,
1164, 1093, 1061, 958, 876, 765.
13C NMR (DMSO-d6) (
d
: ppm): 161.48, 154.52, 145.43, 137.86,
1H NMR (DMSO)
(d: ppm): 11.48 (bs, 4H, eNH), 8.55
137.05, 135.74, 131.67, 129.41, 129.10, 128.93, 128.53, 128.08, 127.76,
123.70, 123.04, 121.21, 117.45, 116.63, 116.11, 109.12.
(bs 6 H/AreH); 8.15 (bm 9 H/AreH); 8.0e7.7 (bm 11H/AreH);
7.7e7.18 (bm 36 H/AreH); 6.95 (s 2H/AreH); 6.55 (s 2 H/AreH);
6.5 (s 2 H/AreH).
MS (ESI), (m/z): Calculated: 438.48; Found: 439.29 [M þ H]þ.
MS (ESI) (m/z): Calculated: 1810.6; Found: 1811.6 [M þ H]þ.
2.1.2. Synthesis metal free phthalocyanine (4)
UVevis (DMSO) lmax/nm [(10ꢁ5 , dm3 molꢁ1 cmꢁ1)] : 672
3
Compound (3) (0.2 g, 0.45 mmol), 1.8-diazabicyclo [4.5.0]
undec-7-ene (DBU) (3 drops) and dry N,N dimethyl aminoethanol
(DMAE) (4 ml) were added in a Schlenk tube. The mixture was
heated and stirred at 160 ꢀC for 24 h under N2 atmosphere. After
cooling to room temperature, the reaction mixture refluxed in
methanol (30 ml) to precipitate the product which was than filtered
off. The green solid product was washed with hot ethanol, acetone
(4.73), 606 (4.02), 332 (4.28).
2.1.3.3. Synthesis of Co (II) phthalocyanine (7). Eluent
for column chromatography: chloroform:methanol (100:5).
Yield: 81 mg (40%), mp > 300 ꢀC.
Anal.calc. for C116H74N16O4: C, 76.58; H, 3.99; N, 12.32.
Found: C, 77.01; H, 3.87; N, 12.01.

H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
3
IR (KBr tablet) ymax/cmꢁ1: 3048, 1603, 1486, 1468, 1403, 1233,
1163, 1091, 1051, 950, 869, 832, 765.
(TD-DFT) with PCM (Polarized continuum model) at the same level
of theory and basis set for 50 singlet transitions in DMSO.
MS (ESI) (m/z): Calculated: 1811.5; Found: 1812.7 [M þ H]þ.
UVevis (DMSO) lmax/nm [(10ꢁ5
3
3. Results and discussion
(4.83), 608 (4.06), 352 (4.42).
3.1. Synthesis and spectroscopic characterization
2.1.3.4. Synthesis of Cu (II) phthalocyanine (8). Eluent
for column chromatography with chloroform:methanol (100:3).
Yield: 90 mg (44%), mp > 300 ꢀC.
of the compound (3) via complementary techniques
The synthetic route of compounds (1e4) is depicted in
Fig. 1. Nucleophilic aromatic nitro displacement reaction of
4-nitrophthalonitrile with base catalyst has been carried out by
many scientists [14,43]. Generally, nucleophilic substitution of
a nitro group from an activated aromatic substrate can be effec-
tively conducted by variety of strong nucleophiles under dipolar
aprotic conditions, for example in DMF or DMSO [43]. In this
respect, initial phthalonitrile derivative (3) was obtained from
reaction between compound (1) and 4-nitrophthalonitrile (2) in
dry DMF at 55 ꢀC. Dry K2CO3 was used for supplying basic reaction
condition. After the crystallization of compound (3), yield of the
product was moderate. All spectral data supported the proposed
structure (3). According to IR spectral data, new vibration that
appeared at 2231 cmꢁ1 clearly indicated that structure (3) contains
nitrile group. Detailed IR analysis (experimental and theoretical) for
the compound (3) is given in Section 3.1. In 13C NMR of (3), the new
peaks at 116,63 ppm and 116,11 ppm belonging to nitrile carbons
were evidence of the substitution. Mass spectral analysis of
compound (3) showed that target compound was successfully
prepared. Stable molecular ion [M þ H]þ peak was seen at 439.29 in
mass spectra of the compound (3). Also elemental analysis data of
compound (3) was satisfactory.
Anal.calc. for C116H74N16O4: C, 76.66; H, 3.99; N, 12.33.
Found: C, 76.78; H, 3.91; N, 12.29.
IR (KBr tablet) ymax/cmꢁ1: 3057, 1602, 1474, 1449, 1405, 1235,
1165, 1095, 1053, 950, 874, 834, 769.
MS (ESI) (m/z): Calculated: 1815.5; Found: 1816.7 [M þ H]þ;
1880.5 [M þ ACN þ Na]þ.
UVevis (DMSO) lmax/nm [(10ꢁ5 , dm3 molꢁ1 cmꢁ1)] : 676
3
(4.80), 608 (4.12), 342 (4.45).
2.2. Crystal structure of the compound (3)
For the crystal structure determination, the single crystal of the
compound 3 was used for data collection on a four-circle Rigaku
R-AXIS RAPID-S diffractometer (equipped with a two-dimensional
area IP detector). The graphite-monochromatized Mo Ka radiation
(
l
¼ 0.71073 Å) and oscillation scans technique with Du ¼ 5ꢀ for
each image were used for data collection. The lattice parameters
were determined by the least-squares methods on the basis of all
reflections with F2 > 2 (F2). Integration of the intensities, correc-
s
tion for Lorentz and polarization effects and cell refinement was
performed using CrystalClear (Rigaku/MSC Inc., 2005) software
[45]. The structures were solved by direct methods using
SHELXS-97 [46] and refined by a full-matrix least-squares proce-
dure using the program SHELXL-97 [46]. H atoms were positioned
geometrically and refined using a riding model. The final difference
Fourier maps showed no peaks of chemical significance. Crystal
data for compound 3: C29H18N4O, crystal system, space group:
orthorhombic, Pbna; (no:60); unit cell dimensions: a ¼ 8.8175(2),
b ¼ 17.4971(2), c ¼ 31.4846(4) Å, volume: 4857.5(1) Å3; Z ¼ 8;
3.2. Description of the crystal and optimized structure
of the compound (3)
The ORTEP plot of title compound is shown in Fig. 2. Selected
bond lengths and bond angles of the structure and the DFT calcu-
lation are compared in Table 1. The compound crystallizes in the
orthorhombic space group Pbna (no:60), with eight molecules in the
unit cell. It consists of 4-(4,5-Diphenyl-1H-imidazol-2-yl)-phenol
and phthalonitrile units. The bond lengths of cyano, C^N in the
structure are in range of 1.134e1.143 Å.
Imidazole and C16/C21 phenyl rings are not strictly planar. They
are considerably strained due to the substituted units. Dihedral
angle formed by LSQ-planes is 21.51(2)ꢀ.As shown in Fig. 3, in the
crystal, the NeH N intermolecular hydrogen bonds are formed
along the b-axis between the imidazole groups of neighboring
molecules [N3/N4i; 2.931(4) Å, N3eH3N; 0.86 Å, N3/H3NeN4;
155ꢀ, symmetry code; (i) 1/2 þ x,y, 1/2-z ].
calculated density: 1.20 g/cm3; absorption coefficient: 0.075 mmꢁ1
;
F(000): 1824;
method: full-matrix least-square on F2; data/parameters:
4974/308; goodness-of-fit on F2: 1.000; final R indices [I > 2
(I)]:
q
-range for data collection 2.3e26.5ꢀ; refinement
s
R1 ¼ 0.058, wR2 ¼ 0.135; R indices (all data): R1 ¼ 0.166,
wR2 ¼ 0.189; largest diff. peak and hole: 0.143 and ꢁ0.164 e Åꢁ3
;
Crystallographic data were deposited in CSD under CCDC registra-
tion number 837496. These data can be obtained free of charge
from The Cambridge Crystallographic Data Center via www.ccdc.
cam.ac.uk/data_request/cif.
Geometrical parameters obtained from the computational study
are acceptable when compared with the crystallographic results
except for N3eH bond length and some dihedral angle. While
N3eH bond length was found 0.859 A in crystallographic study, it
was calculated as 1.010 A. This difference in the N3eH bond length
may have brought about different N3eH vibrational frequencies in
the experimental and theoretical vibrational spectra (in section
3.3.1). Most probably, the difference between the theoretical and
experimental N3eH bond length is caused by intermolecular
hydrogen bonding and molecular packing that was not considered
in the theoretical calculation.
2.3. Computational details
The molecular geometry of the compound (3) was optimized by
using the DFT method with a hybrid functional B3LYP (Becke’s
three parameter hybrid functional using the LYP correlation func-
tional) and the 6-311G(d)þ basis set [47,48]. All calculations were
performed with the Gaussian 03W [44] software package. The
harmonic vibrational frequencies were calculated at the same level
of the theory for the optimized geometry of the compound (3).
Absence of the imaginary frequency indicated that the structure
was in global minimum and obtained vibrational frequencies were
scaled by 0.9613 [49]. Vibrational frequency assignments were
done by using Gauss-view molecular visualization software [50].
Tight convergence criterions were used at the geometric optimi-
zation and frequency calculation. Electronic absorbtion properties
were studied using time-dependent density functional theory
3.3. Assignments of the vibrational modes of the compound (3)
The theoretical vibrational spectrum of substituted phthaloni-
trile ligand (3) was calculated using B3LYP method with 6-311G(d)þ
basis set [47,48]. The theoretical results of the compound (3) were

4
H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
N
N
C
N
N
C
N
-
r
D y DMF K
2CO3
N
H
O
+
O
550C
N
H
N
O2
C
N
H
C
3
2
1
0
DMAE/DB
U-160
C
HN
N
N
N
H
O
O
N
N
N
N
M
N
N
N
N
O
H
N
O
N
N
NH
4
5
6
7
8
Cu
M
Zn Ni
Co
2H
Fig. 1. Synthetic route for novel compounds.
compared with the experimental results. The vibration band
assignments were studied by using Gauss-View molecular visuali-
zation program [50]. The frequency values computed at the calcu-
lation level contain known systematic errors. Therefore, 0.9613 was
selected as the scaling factor [49]. Selected theoretical and experi-
mental vibrational data are shown in Table 2. Selected vibrational
frequencies have good correlation with corresponding experi-
mental results except for N3-H stretching vibration as can be seen
in Fig. 4.
phase. Imidazole derivatives contain strong intermolecular
hydrogen bonds in solid phase. Although free NeH stretching
vibration was expected to be about 3400 cmꢁ1
,
N3eH
stretching vibration shifts to aromatic CeH stretching range
Table 1
Some selected geometrical parameters compared with crystallographic data.
Bond lenght A
X-ray
Calc.
Bond angle (ꢀ)
X-ray
Calc.
N3eH
N3eC8
0.859
1.371
1.361
1.393
1.328
1.360
1.401
1.383
1.470
1.471
1.436
1.143
1.392
1.452
1.368
1.373
1.436
1.389
1.383
1.385
1.378
1.374
1.371
1.134
1.008
1.383
1.369
1.375
1.319
1.363
1.395
1.393
1.468
1.473
1.427
1.155
1.404
1.462
1.402
1.393
1.431
1.399
1.391
1.390
1.397
1.389
1.393
1.154
HeN3eC8
N3eC8eC7
N3eC15eN4
N4eC7eC8
125.4
104.8
110.4
109.9
118.8
115.5
119.9
134.5
131.3
121.4
119.7
124
124.0
104.5
110.2
109.7
120.1
115.5
118.9
134.8
130.2
122.2
120.4
124.6
118.8
119.8
120.2
119.5
Calc.
175.8
ꢁ174.7
136.5
8.4
ꢁ176.7
140.6
ꢁ5.2
3.3.1. CeH and NeH vibrations
The experimental and theoretical FTeIR spectra of the
compound are shown in Fig. 5. Some imidazole derivatives in solid
phase show crystal interactions in vibrational spectra. Because of
these interactions, some frequencies can be different from the gas
N3eC15
N4eC7
N4eC15
O1eC22
O1eC19
C8eC7
N4eC7eC6
O1eC22eC27
O1eC19eC18
C7eC8eC9
C8eC7eC6
C7eC6eC5
C8eC9
C7eC6
C29eC25
C29eN2
C14eC9
C16eC15
C16eC17
C26eC27
C26eC28
C25eC24
C17eC18
C10eC11
C22eC27
C18eC19
C13eC12
C28eN1
C8eC9eC14
N3eC15eC16
C15eC16eC21
C29eC25eC24
C27eC22eC23
C10eC11eC12
Dihedralangle (ꢀ)
C19eO1eC22eC27
O1eC19eC20eC21
C10eC9eC8eN3
C21eC16eC15eN4
C9eC8eN3eC15
C14eC9eC8eC7
C9eC8eC7eC6
119.7
119
120
119.8
X-ray
ꢁ173.7
ꢁ176.5
141.2
21.2
ꢁ177.7
147.1
ꢁ6.1
Fig. 2. Crystal sturucture of the compound (3).

H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
5
Fig. 3. Unit cell of the compound (3) view down along the b-axis.
(3100e3000 cmꢁ1) because of the strong intermolecular hydrogen
bonding causing polymeric association through imidazole rings
[51,52]. The theoretical NeH stretching vibration was observed at
3506 cmꢁ1 because the theoretical vibration calculation was per-
formed for a single molecule in vacuum media.
The aromatic structures show characteristic CeH stretching
vibrations at 2900e3150 cmꢁ1 range. In the present study,
there were many aromatic CeH stretching vibrations at around
3100e2900 range in the experimental IR spectra, the superimpo-
sition of the aromatic CeH stretching vibrations resulted in broad
absorption band. Similarly, according to theoretical data, many
aromatic CeH stretching vibrations as well known “group
frequencies” were observed at around 3090e3034 cmꢁ1 [49,53].
The aromatic structures show CeH in plane bending and CeH
out of plane bending vibrations in the range of 1300e1000
and 1000e750 cmꢁ1 respectively. CeH in plane bending
Table 2
Experimental and calculated vibrational assignments of the compound (3).
Vibrational mode
Vibrations (Exp). cmꢁ1
Vibrations (theo.)
Intensity
scaled 0.9613 cmꢁ1
y
(N3eH)
ysym CeH (C23eH) þ (C24eH)
CeH (C27eH)
ysym CeH (C21eH)þ (C20eH)
CeH (C14eH), (C13eH), (C12eH), (C11eH), (C10eH)
yasym. CeH (C21eH), (C20eH)
3506
3090
3089
3087
3064
3063
3058
3053
3045
3044
2251
2244
1590
1585
1582
1574
1531
1503
1462
36.7
0.8
1.0
y
1.5
y
3057
3049
39.9
12.5
52.3
25.6
15.4
25.8
21.3
84.3
93.1
29.4
41.7
374.2
154.6
219.9
827.0
y
y
CeH (C5eH), (C4eH), (C3eH), (C2eH), (C1eH)
CeH (C14eH), (C13eH), (C12eH), (C11eH), (C10eH)
yasym CeH (C1eH), (C2eH), (C4eH), (C5eH)
yasym CeH (C17eH), (C18eH)
y
y
y
y
y
y
y
y
y
C28^N1 (meta position)
C29^N2 (para position)
C]C (C17eC18), (C20eC21)
C]C (C1eC2), (C4eC5)
2231
C]C (C10eC11), (C13eC14)
C]C (C23eC24), (C26eC27) þ
y
C15 ¼ N4(imidazole ring)
C15 ¼ N4 (imidazole ring) þ
1595
1563
1542
1482
C]C (C26eC25),(C22eC23),(C7eC8),
y
b (N3eH)
C]C (C19eC20), (C17eC16), (C7eC8) (C16eC15)
C]C (C26eC25) þ CeH (C14eH), (C13eH), (C12eH), (C11eH), (C21eH),
(C20eH), (C17eH), (C18eH), (C27eH), (C23eH)
C]C (C27eC26) þ CeH (C23eH)
CeH (C27eH),(C23eH), (C24eH)
b
Ar
y
b
1423
1288
1250
1393
1259
1224
190.0
669.2
1353.8
y
b
b
CeO (O1eC22) þ
b
CeH (C27eH), (C24eH) þ
y
y
CeO (C22eO1)
CeO. (C19eO1)
y
CeH (C27eH), (C24eH) þ
Phenyl ring breathing mode þ
(C7eN4) þ
b
CeH (C5eH), (C4eH), (C3eH),
1213
1185
767.7
(C2eH), (C10eH), (C11eH), (C3eH)
b
b
CeH (C17eH), (C18eH), (C21eH), (C20eH),(C27eH), (C23eH), (C24eH) þ
1173
1087
1149
1070
161.6
60.0
CeH (C17eH), (C18eH), (C21eH), (C20eH), (C1eH), (C3eH) (C4eH)
(C13eH) þ
b
(N3eH) þ Ar CeCeC in plane bending
b
CeH (C14eH), (C13eH), (C12eH), (C11eH), (C10eH), (C1eH) (C3eH) (C4eH) þ
b
(N3-H)
1062
1017
953
857
833
767
696
1058
992
934
835
814
747
681
678
Ar CeCeC in plane bending
51.8
195.4
180.0
138.6
267.3
255.3
264.2
g
u
g
g
u
u
CeH (C27eH), (C23eH), (C24eH) þ Ring breathing
CeH (C21eH), (C17eH), (C20eH), (C18eH)
CeH (C27eH), (C23eH), (C24eH)
CeH (C14eH), (C11eH), (C2eH), (C3eH), (C4eH)
(C6eC14) phenyl ring
(C15eC1) phenyl ring
n: stretching,b: in plane bending, g:out of plane bending, u: out of plane wagging.

6
H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
The CeCeC in plane bending and ring breathing mode of
benzene are observed at 1010 cmꢁ1 and 992 cmꢁ1. These vibrations
calculated at 1017 and 953 cmꢁ1 respectively were in agreement
with the experimental results at 992 and 934 cmꢁ1 [54,56,58].
3.3.3. CeN and CeO vibrations
The experimental C^N stretching mode was observed at
2230 cmꢁ1 as a single sharp band while in theoretical C^N
stretching vibrations were observed as a sharp and intense band at
2244 and weak shoulder at 2251 cmꢁ1 [57]. The low intense band at
2251 cmꢁ1 was not observed in the experimental spectrum. The
reason for this may be the proximity of the 2244 and 2251 cmꢁ1
bands causing them seem as a single band. Due to the dense C]C
phenyl stretching vibrations, C]N stretching vibrations were
observed together with C]C aromatic stretching vibrations at 1574
and 1531 cmꢁ1 [52,54,57].
Fig. 4. Correlation between experimental and calculated vibrational data of the
compound (3).
C
AreO stretching vibrations calculated at the range of
1224e1149 cmꢁ1 were in good agreement with the experimental
data and literature [57].
vibrations were calculated at 1393, 1259, 1224, 1185, 1149,
1070 cmꢁ1. The vibrations calculated at 934, 835, 814, 747 cmꢁ1
were assigned to CeH out of plane bending vibrations. All experi-
mental CeH vibrations were in good agreement with the theoret-
ical results [52,54e56].
3.3.4. Electronic absorption spectra of the compound (3)
Electronic absorption spectrum of the compound (3) was
recorded in the 200e600 nm range in DMSO and absorption
bands were observed at 224, 263 and 321 nm in UV region,
respectively (Fig. 6). In order to explain electronic transition and to
compare with the experimental spectrum, TD-DFT study was
performed for 50 singlet transitions. The solvent effect on the
theoretical electronic transitions was studied with the PCM
(polarized continuum model) in DMSO. The computed electronic
transition values, such as absorption wavelength, oscillator
strengths and experimental values are given in Table 3. As can be
seen in the theoretical and experimental results, since there is no
transition in visible region, compound (3) is colorless. On the
3.3.2. C]C aromatic ring vibrations
Aromatic C]C stretching vibrations of the phenyl ring appeared
in the range of 1625e1430 cmꢁ1. In our study, the frequencies were
observed at 1574, 1531, 1503, 1462, 1393 cmꢁ1 theoretically and
at 1595, 1563, 1542, 1482, 1423 cmꢁ1 experimentally. Generally
determination of the C]N aromatic vibrations are difficult; several
vibrational types are seen in the region of the aromatic
carbonecarbon ring vibration. C]C aromatic stretching vibrations
calculated at a range of 1574e1393 cmꢁ1 were in good agreement
with the experimental data at a range of 1595e1423 cmꢁ1. Due to
the dense C]C phenyl stretching vibrations, C]N stretching
vibrations were observed together with C]C aromatic stretching
vibrations at 1574 and 1531 cmꢁ1 [52,54,57].
Fig. 5. Theoretical and experimental vibrational spectra of the compound (3).
Fig. 6. Theoretical and experimental UVevis spectrum of the compound (3) in DMSO.

H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
7
Table 3
Experimental and theoretical transitions and orbital contributions.
Experimental
transitions
Theoretical transitions
Wavelength log
(nm)
3
Wavelength
(nm)
Oscillator Electronic transition modes
strength
and orbital contributions
224
4.43 220.2
0.3721
H-4 / Lþ3 (19%)
H-7 / Lþ2 (18%)
H-6 / L (11%)
H-5 / Lþ2 (7%)
H-4 / Lþ3 (30%)
H-3 / Lþ3 (28%)
H-4 / Lþ2 (11%)
H-3 / Lþ1 (27%)
H-5 / Lþ1 (22%)
H-6 / Lþ1 (11%)
H-6 / L (6%)
220.8
232.0
0.1462
0.1712
H-6 / Lþ2 (5%)
H-3 / Lþ2 (5%)
H-1 / Lþ2 (60%)
H-1 / Lþ2 (25%)
H-1 / Lþ1 (33%)
H / Lþ3 (97%)
H / Lþ2 (83%)
H / Lþ1 (83%)
H / L (99%)
263
321
4.05 247.2
253.4
0.22
0.34
4.23 303.8 (4.09ev) 0.36
326.7 (3.80ev) 0.48
332.3(3.74ev)
407.5 (3.05ev) 0.02
0.43
contrary to the theoretical spectrum, absorbtion band about at
400 nm was not seen in experimental spectrum. This situation can
be explained by very low oscillator strength of the corresponding
transition [55].
Fig. 7. Some important electronic transition of the compound (3).
The HOMO (highest occupied molecular orbital) and LUMO
(lowest unoccupied molecular orbital) called as frontier orbitals
determine the chemical reactivity of the compound. HOMO orbitals
are nucleophilic center while LUMO orbitals are electrophilic center
and the gap between the energy of HOMO and LUMO determine
the chemical stability of the compound [58]. 3D plots of some
important HOMOs and LUMOs of the compound (3) are shown in
Fig. 7. As can be seen in Fig. 7, the HOMO orbital is localized on the
phenyl and especially imidazole ring and LUMO orbital is localized
on the phthalonitrile ring.
The 1H NMR spectra of (7) and (8) could not be determined
because of the presence of paramagnetic cobalt and copper ions
1
[64]. The H NMR spectra of phthalocyanines (4), (5) and (6) were
obtained in DMSO-d6 at room temperature. The spectra of the
compounds were very similar. In 1H NMR spectra, except for NeH
protons of imidazole moieties, all protons were observed at
aromatic region. For metal free phthalocyanine (4), imidazole NeH
protons were observed at 11.19 ppm as a broad singlet and the
typical shielding of inner core protons could not be observed due to
the strong aggregation between phthalocyanine molecules [65]. For
ZnPc (5) and NiPc (6) respectively, imidazole NH protons were
observed at 12.71 ppm and 11.48 ppm as broad singlets and other
protons were observed at aromatic region. In addition, mass spectra
and elemental analysis results of the compounds (4e8) were in
good correlation with proposed structure.
3.3.5. Synthesis of metal free (4) and metallophthalocyanines (5e8)
Although there are many synthetic methods for preparing
substituted phthalocyanines in literature [59e62] authors gener-
ally prefer cyclotetramerization of substituted phthalonitrile
or 1,3-diimino-1H-isoindoles [14,63]. Peripherally substituted
phthalocyanines are prepared from the cyclotetramerization of
4-substituted phthalonitrile and non-peripherally substituted
phthalocyanines are prepared from 3-substituted ones. Tetra
substituted phthalocyanines prepared from either 4-substituted or
3-substituted phthalonitriles are obtained as a mixture of four
different possible isomers (C4h, C2v, Cs and D2h).
3.3.6. UVevis absorption spectra of the compound (4e8)
All of the phthalocyanines were soluble in most of the organic
solvents such as chloroform, THF, dichloromethane, DMF, DMSO
and pyridine. For the metallophthalocyanines (5e8) in DMSO, the Q
bands caused by
p / p* transitions were observed at 680, 672, 676
and 676 nm respectively (Figs. 8 and 9). The shoulders neighboring
the Q band of these metallophthalocyanines were observed at: 612
for (5) ,606 for (6), 608 for (7) and 608 for (8). For Q band regions of
metallophthalocyanines, the longer wavelength absorptions are due
to the monomeric species and shorter wavelength absorptions
(shoulders) are due to the aggregated species [66]. So, in DMSO at
1 ꢂ 10ꢁ5 mol dmꢁ3 concentration, monomeric behavior of metal-
lophthalocyanines was proved by the dominance of the longer
In this study, 4-substituted phthalonitrile (3) was used as the
initial compound for synthesis of the metal-free- and metal-
lophthalocyanines (Zn, Ni, Co, Cu) and no effort was given to
separate the isomeric mixture. All new phthalocyanines were
characterized by IR, 1H NMR, mass spectrometry, elemental anal-
ysis and UV/Vis. All spectral data in Section 2 support the proposed
structures (4e8). In the IR spectra of all novel phthalocyanines,
the eC]N vibration of compound (3) disappeared, the absence
of eC]N vibration in the phthalocyanine IR spectral data supports
the proposed target structures. The rest of the spectra are similar to
that of compound (3). The main difference between the IR spectral
data of metal-free and metallophthalocyanines is the inner
core eNH vibration for metal free phthalocyanine (4) that was
wavelength absorptions. The B bands arising from deeper
p levels
to LUMO were observed at: 357, 332, 352 and 342 nm for (5, 6, 7)
and (8) respectively (Figs. 8 and 9). Differently from metal-
lophthalocyanines, the Q band absorption of metal-free phthalo-
cyanines splits into two strong absorption bands as Qx and Qy in
visible region. In DMSO, the splitting Q band absorption of
compound (4) was observed at 698 and 664 nm with shoulders at
observed at 3285 cmꢁ1
.

8
H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
Fig. 10. UVevis spectra of compound (4) in DMSO at 1 ꢂ 10ꢁ5 mol dm-3.
Fig. 8. UVevis spectra of compound (6), (7) and (8) in DMSO at 1 ꢂ 10ꢁ5 mol dmꢁ3
.
642 and 598 nm, which is an evidence of non-degenerate D2h
symmetry. Additionally, B-band of compound (4) was observed at
342 nm (Fig. 10).
the Q band is observed as a sharp peak with a shoulder at the higher
energy side, while for aggregated species, the shoulder shifts to red
with increasing intensity and Q band is observed as a broad peak
with lower intense. In consequence, ZnPc (5) showed monomeric
behavior in DMSO, DMF, THF, pyridine and dioxane and aggregated
in chloroform, benzene, 1,2-dichloroethane, dichloromethane and
toluene at a concentration of 1 ꢂ 10ꢁ5 mol dmꢁ3 (Fig. 11).
Guttmans donor and acceptor number are used to explain lewis
basicty and acidity of the solvents [68]. The aggregation behavior of
the compound (5) in different solvents are closely related with
donor and acceptor number. According to the spectroscopic data,
aggregation was not observed in the solvents that donor number is
higher than acceptor number. On the contrary, in solvents that
acceptor number higher than donor number, aggregation was
observed (Table 4). Possible causes for this situation is strong
interaction between metal center (Zn) and solvent molecules with
electron donor character.
Aggregation, usually defined as a coplanar association of rings
from monomer to dimer or higher order complexes, is dependent on
the concentration, nature of the solvent, nature and connection of
the substituents, coordinated metal ions and temperature [67]. The
aggregation behavior of the zinc(II)phthalocyanine (5) was investi-
gated at different concentrations in DMSO and also in different
solvents (Figs. 9 and 11). The intensity of Q-band maxima is directly
proportional with the concentration and no new band that was sign
of aggregation was observed. The zinc(II)phthalocyanine did not
show aggregation and BeereLambert law was obeyed between the
concentrations 1.6 ꢂ 10ꢁ5 and 4 ꢂ 10ꢁ6 mol dmꢁ3(Fig. 9).
The absorbtion spectra of zinc(II) phthalocyanine (5) in different
solvents at 1 ꢂ10ꢁ5 mol dmꢁ3 concentration are shown in Fig. 11. In
the absorbtion spectra of phthalocyanines; for monomeric species,
Fig. 9. Absorption spectra of the compound (5) in DMSO at different concentrations.

H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
9
Fig. 11. Absorption spectra of the compound (5) in different solvents. Concentration ¼ 1 ꢂ 10ꢁ5 mol dmꢁ3
.
Zn(II) phthalocyanines ring system has four nitrogen atoms
called “meso-nitrogens”. These nitrogens can be protonated in
acidic media. Mono-, di-,triprotonation of the nitrogen atoms cause
decrease in the symmetry. The Q band splits and a new band
appears in the bathochromic region. Tetraprotonation of zinc
phthalocyanine reverts back to D4h symmetry, but the Q band is
still red shift. The shift of the Q band to red is an important
property for photodynamic therapy (PDT) and photo sensing
application. Peripherally substituted phthalocyanines isn’t resis-
tant against high concentration of sulfuric acid, so their “di-”, “tri-”,
“tetra-” protonated forms cannot be prepared [69,70]. In our
study, we investigated protonation behavior of the compound (5)
by using sulfuric acid in DMSO. We studied on five
Table 4
Donor and acceptor number of some solvents [68].
Solvent
Donor number
Acceptor number
Compound (5) in
solution
Pyridine
DMSO
DMF
Dioxane
THF
Dichlorometan
Toluene
Benzene
1,2-dichloroethane
Chloroform
33.1
29.8
26.6
14.3
20.0
1.0
0.1
0.1
0
14.2
19.3
16.0
10.3
8.0
20.4
8.2
8.2
Non-aggregate
Non-aggregate
Non-aggregate
Non-aggregate
Non-aggregate
Aggregate
Aggregate
Aggregate
Aggregate
Aggregate
16.7
23.1
0
different solutions containing 10ꢁ6
M compound (5) and
0.47e0.98e1.88e2.35e2.82 M sulfuric acid respectively. As can be
seen in Fig. 12, while the Q band intensity was decreasing, the
intensity of the new bathochromic band was increasing because of
the first protonation of the compound (5). When sulfuric acid
concentration was increased above 2.82 M, compound (5) began to
decompose so, di-, tri-, and tetra- protonation forms of compound
(5) couldn’t be obtained.
4. Conclusion
In this paper, we report the preparation of a new type of metal
free and metallophthalocyanines (Zn, Ni, Co and Cu). At first stage,
compound (3) was synthesized from a mixture of (1) and (2) (1:1)
in the presence of DMF/K2CO3 and obtained as single crystal form
suitable for X-ray analysis. In addition, geometric structure of the
compound (3) was optimized theoretically and compared with the
X-ray crystallographic data. Vibrational assignments and electronic
transitions of the compound (3) were calculated and compared
with the experimental results. It was found that the theoretical
results agreed with the experimental results. In the final stage,
metal free and metallophthalocyanines were synthesized by the
interaction of the compound (3) in DMAE/DBU and corresponding
Fig. 12. Spectral changes for the first protonation of compound (5) increasing
concentration of H2SO4 in DMSO. H2SO4 concentrations as follows: 0.47, 0.94, 1.88,
2.35, 2.82 mol dmꢁ3
.

10
H.T. Akçay et al. / Journal of Organometallic Chemistry 713 (2012) 1e10
[31] Q. Zhao, S.J. Liu, M. Shi, F.Y. Li, H. Jing, T. Yi, Organometallics 26 (2007)
5922e5930.
metal salts. The structures of the new products (3e8) are charac-
terized by elemental analysis, IR, UVevis, 1H NMR and Mass spec-
trometry. Furthermore, aggregation behavior of the compound (5)
was researched in different solvents and also at different concen-
trations in DMSO. Substituted ZnPc (5) aggregated in chloroform,
dichloromethane, 1,2-dichloroethane, benzene and toluene, while
non-aggregated in DMSO, DMF, pyridine, THF, dioxane at
1 ꢂ 10ꢁ5 mol dmꢁ3 concentrations. The effect of the solvent
donor and acceptor number to aggregation behavior of the
compound (5) was investigated. It was observed that there was no
aggregation in solvents of higher donor number. ZnPc (5) showed
monomeric behavior between the concentrations of 4 ꢂ 10ꢁ6
and 16 ꢂ 10ꢁ6 mol dmꢁ3 in DMSO. The protonation behavior of the
compound (5) in acidic media was studied at different sulfuric acid
concentration in DMSO. The new band observed about at 720 nm in
UV-vis spectrum of the compound (5) was evidence that one of the
meso nitrogens on the phthalocyanine ring system was protonated.
Once the concentration of the sulfuric acid in the solution was
higher than 2.82 M, as expected, abnormal bands observed in the
spectrum were signs of the decomposition of the compound (5).
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Acknowledgment
This study was supported by Karadeniz Technical University -
Research Funding - (Project no 2008.111.02.2).
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