Synthesis and computational studies of new metallo-phthalocyanines bearing dibenzoxanthenes and evaluation of their optical properties in solution and solid PMMA/ZnPc/Al nanocomposite films

Article abstract of DOI:10.3906/kim-1509-28

New thermally stable metallo-phthalocyanines bearing dibenzoxanthenes as highly organo-solubilizing aromatic hydrocarbon substituents were successfully prepared by cyclotetramerization of corresponding phthalonitriles with anhydrous metal salts [Zn(CH₃ COO)₂ and NiCl₂] in the presence of a catalytic amount of DBU in 2-(dimethylamino) ethanol. All of these phthalocyanines are soluble in some organic solvents such as DMF, DMSO, THF, CH₂ Cl₂, and CHCl₃. Then we successfully prepared the poly(methyl methacrylate) (PMMA)/ZnPc/Al nanocomposite films by incorporating Al nanoparticles into a transparent PMMA/ZnPc matrix. The structure and morphology of nanocomposite films were studied using X-ray diffraction and scanning electron microscopy. The optical absorption spectra of PMMA/ZnPc/Al nanocomposite films showed red shifting in the Q-band in the polymeric matrix. The geometrical structure of two phthalocyanines was investigated at the RHF/3-21G? computational level.

Full text of DOI:10.3906/kim-1509-28

Turk J Chem
Turkish Journal of Chemistry
(2016) 40: 602 – 612
¨
http://journals.tubitak.gov.tr/chem/
˙
c
⃝ TUBITAK
doi:10.3906/kim-1509-28
Research Article
Synthesis and computational studies of new metallo-phthalocyanines bearing
dibenzoxanthenes and evaluation of their optical properties in solution and solid
PMMA/ZnPc/Al nanocomposite films
Ali Reza KARIMI1,∗, Zeinab JAFARZADEH1, Meysam SOURINIA1,
Akbar ZENDEHNAM2, Azam KHODADADI1, Zeinab DALIRNASAB1,
Mohammad SOLIMANNEJAD1, Peyman ZOLGHARNEIN3
1Department of Chemistry, Faculty of Science, Arak University, Arak, Iran
2Department of Physics, Faculty of Science, Arak University, Arak, Iran
3Department of Materials Science and Engineering, Faculty of Engineering, Sheffield University,
Sheffield, United Kingdom
Received: 13.09.2015
•
Accepted/Published Online: 12.01.2016
•
Final Version: 21.06.2016
Abstract: New thermally stable metallo-phthalocyanines bearing dibenzoxanthenes as highly organo-solubilizing aro-
matic hydrocarbon substituents were successfully prepared by cyclotetramerization of corresponding phthalonitriles with
anhydrous metal salts [Zn(CH3 COO)2 and NiCl2 ] in the presence of a catalytic amount of DBU in 2-(dimethylamino)
ethanol. All of these phthalocyanines are soluble in some organic solvents such as DMF, DMSO, THF, CH2 Cl2 ,
and CHCl3 . Then we successfully prepared the poly(methyl methacrylate) (PMMA)/ZnPc/Al nanocomposite films by
incorporating Al nanoparticles into a transparent PMMA/ZnPc matrix. The structure and morphology of nanocom-
posite films were studied using X-ray diffraction and scanning electron microscopy. The optical absorption spectra of
PMMA/ZnPc/Al nanocomposite films showed red shifting in the Q-band in the polymeric matrix. The geometrical
structure of two phthalocyanines was investigated at the RHF/3-21G* computational level.
Key words: Soluble metallophthalocyanine, dibenzoxanthene, aggregation, nanocomposite film, geometry optimization
1. Introduction
For many years, phthalocyanines have been used as pigments.1 Recently, Pc complexes have been investigated
in diverse fields such as solar cells,2 photovoltaic cells,3 semiconductor devices,4 electrochromic displays,5
photodynamic therapy (PDT),6,7 optical disks,8 gas sensors,9 chemical sensors,10 liquid crystals,11 film
materials,12 laser dye,13 nonlinear optics,14 and various catalytic processes.15,16
Stability and solubility are the main key factors to determine the functionality of a dye. Recently, synthesis
of dye-based black matrix (BM), a component of LCD color filters, has been attracting extensive interest.17,18
However, dyes as color filters are not widely used for commercial applications due to their unsatisfactory thermal
stability and solubility. Therefore, the dyes for BM should have good solubility in industrial solvents and they
need to be structurally stable.
Changing the substituents at the periphery of the benzene rings can significantly affect the physico-
chemical properties of phthalocyanine compounds.19−25 This substitution gives flexibility in solubility and also
∗Correspondence: a-karimi@araku.ac.ir
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KARIMI et al./Turk J Chem
efficiently tunes the color of the phthalocyanines. Substitution of functional groups also changes the elec-
tron density of Pcs and finds use in various fields. The synthesis of xanthenes, especially benzoxanthenes,
with biological and therapeutic properties such as antibacterial,26 anti-inflammatory,27 and antiviral28 has at-
tracted significant interest. Furthermore, these heterocyclic compounds are used as sensitizers in photodynamic
therapy29 and antagonists for the paralyzing action of zoxazolamine.30 Moreover, due to their useful spectro-
scopic properties, they are used as dyes,31 in laser technologies,32 and in fluorescent materials for visualization
of biomolecules.33
Encouraged by this information and due to our interest in the synthesis of Pcs,34−36 herein we report
the preparation of new phthalocyanines (Pcs) containing four dibenzoxanthene groups as substituents on the
zinc phthalocyanine structure to increase the solubility of the studied Pcs (Scheme).
Then we prepared the PMMA/ZnPc/Al nanocomposite films by incorporating Al nanoparticles into
a transparent PMMA/ZnPc matrix. Zinc-phthalocyanine (Zn-Pc) in a polymeric matrix was amplified with
various loadings (5%, 10%, and 15%) of aluminum.
Optical properties of thermally stable metallo-phthalocyanines bearing dibenzoxanthenes in solution and
solid PMMA nanocomposite films have been investigated. The PMMA/ZnPc/Al nanocomposite films exhibit
a red shift effect in Q-band absorption of phthalocyanine.
2. Results and discussion
Phthalonitrile derivatives 5a, 5b, and 5c were synthesized in two steps (Scheme). First, dicyano compounds
3a–c were obtained by nucleophilic aromatic nitro displacement on 4-nitrophthalonitrile 1 with hydroxyben-
zaldehydes 2a–c in the presence of anhydrous K2 CO3 as the base in DMF. Then compounds 3a–c were reacted
with two equivalents of β -naphthol under solvent-free conditions in the presence of p-toluene sulfonic acid as
the catalyst.37 Compounds 3a–c were obtained in 90%, 84%, and 81% yields, respectively. The IR spectra of
5a, 5b, and 5c clearly indicate the presence of CN vibrational peaks at 2236, 2231, and 2231 cm−1 , respectively.
The 1 H NMR spectra were also in good agreement with the structures of the compounds 5a, 5b, and 5c. For
instance, the spectrum of 5a exhibited an aliphatic proton as a singlet at δ 6.55 ppm (1H). The aromatic
protons in the low field region appear as two doublets at δ 6.83 (2H) and 7.03 ppm (1H), a singlet at δ 7.16
ppm (1H), a multiplet at δ 7.47–7.89 ppm (13H), and a doublet at δ 8.37 ppm (2H).
The metallophthalocyanines 6–10 were obtained by cyclotetramerization of dinitrile compounds 5a, 5b,
and 5c (3 mmol) in the presence of anhydrous metal salts [NiCl2 and Zn(CH3 COO)2 ] (1 mmol) using DBU
as catalyst. The reaction was carried out in refluxing 2-(dimethylamino)ethanol (DMAE) under a nitrogen
atmosphere. IR, 1 H NMR, MALDI-TOF-MS, and UV-vis spectra confirmed the proposed structures of the
synthesized metallophthalocyanines. Thermogravimetric analysis (TGA) was used for determining the thermal
stability of these complexes. The IR spectra of phthalocyanines 6–10 lacked the CN band completely. The IR
spectra of nanocomposite films showed new peaks attributed to the PMMA matrix. The 1 H NMR spectrum of
7 indicated aromatic protons as multiplets at δ 6.82–8.38 ppm. The aliphatic CH protons appeared at δ 6.55
ppm. In the 1 H NMR spectrum of 8, the aliphatic CH3 group protons appeared at δ 3.57 ppm, protons of
CH groups appeared at δ 6.57 ppm, and aromatic protons were observed as a multiplet at δ 7.05–8.43 ppm.
The MALDI–TOF–MS measurement for compounds 7, 8, and 10 gave the characteristic molecular ion peaks
at m/z: 2061, 2188, and 2067 [M+ ], respectively, confirming the proposed structures.
The thermal behavior of phthalocyanines 7, 8, and 10 was analyzed by TGA in the temperature range
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O
b
O
O
OHC
OH
2
O
3a
O
4
N
CN
NC
CN
a
N
N
N
N
6: M= Zn
7: M= Ni
N
M
N
CN
O
OH
5a
2a
1
OHC
N
+
O
O
CN
CN
c
O2N
O
6-7
O
O
O
b
O
O
OHC
OH
OCH3
2
3b
O
OCH3
O
4
OCH3
N
CN
CN
CN
NC
a
N
N
N
N
8: M= Zn
9: M= Ni
OCH3
N
M
N
O
OH
H3CO
5b
2b
1
OHC
N
H3CO
+
O
O
CN
CN
c
H3CO
O2N
O
O
O
8-9
O
b
O
3c
OH
2
OHC
O
O
O
4
CN
N
CN
NC
OH
a
N
N
N
N
CN
N
N
Zn
N
O
5c
2c
1
OHC
+
CN
CN
O
c
O
O
O2N
O
10
O
Scheme. Synthesis of metallophthalocyanines 6–10. Reagents and conditions: (a) K2 CO3 , DMF, 24 h, rt; (b) Solvent-
free, p-TSA, 125 ◦ C, 20 min; (c) Zn(OAc)2 or NiCl2 , DBU, DMAE, N2 , reflux 18 h. 6: 34%, 7: 36%, 8: 35%, 9: 41%,
10: 33%.
30–1000 ◦ C under a nitrogen atmosphere with a heating rate of 10 ◦ C/min. The first weight loss below 120
◦ C is related to vaporization of trapped solvent such as water or ethanol. Significant loss of weight started after
320 ◦ C. This loss was attributed to a major decomposition reaction between 320 and 800 ◦ C. These results are
summarized in Table 1. The loss of weight at 800 ◦ C was 37% for 7, 55% for 8, and 40% for 10.
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Table 1. Thermal analyses data for 7, 8, 10.
◦
◦
Name Mass loss (up to 300 C) Mass loss (up to 800 C)
7
8
10
3%
5%
3%
37%
55%
40%
The structure and morphology of PMMA/ZnPc/Al nanocomposite films were studied using X-ray diffrac-
tion (XRD) and scanning electron microscopy (SEM). A SEM image of one of the nanocomposite films is shown
in Figure 1. This image exhibited a uniform distribution of aluminum nanoparticles in the polymer matrix.
There it can be seen that the average size of nanocomposite film containing 10% aluminum is 29.8 nm.
XRD patterns of the PMMA/ZnPc/Al nanocomposite films showed four peaks for Al at 38.583◦ , 44.848◦ ,
65.220◦ , and 78.352◦ (Figure 2). Moreover, XRD of nanocomposite films shows two peaks at 2θ: 15◦ and
20◦ that are attributed to the polymeric matrix (Figure 2). The particle size of crystalline aluminum was
determined from XRD details by the Debye–Scherrer equation. The results revealed that the particle size was
less than 100 nm.
Figure 1. Scanning electron microscopy image. PMMA
(0.2 g)/ZnPc 6 (0.01 g)/Al (10%).
Figure 2. XRD spectra of (a) PMMA (0.2 g)/ZnPc 6
(0.01 g); (b) PMMA (0.2 g)/ZnPc 6 (0.01 g)/Al (10%);
(c) PMMA (0.2 g)/ZnPc 6 (0.01 g)/Al (15%).
Furthermore, the surface roughness of nanocomposite films was measured. The results of surface rough-
ness of nanocomposite films are shown in Figure 3 and Table 2. These results indicate the accumulation of
nanoparticles in the nanocomposite films has not been observed and the high percentage of Al nanoparticles
leads to an increase in the roughness of nanocomposite films.
Table 2. The surface roughness of nanocomposite films.
Name Ra (µm) Rq (µm) Rv (µm)
a
b
c
0/240
0/402
1/219
0/300
0/402
1/610
0/615
0/664
2/927
(a) PMMA (0.2 g)/ZnPc 6 (0.01 g)/ Al (5%); (b) PMMA (0.2 g)/ZnPc 6 (0.01 g)/Al (10%); (c) PMMA (0.2 g)/ZnPc
6 (0.01 g)/Al (15%).
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Figure 3. The results of surface roughness of nanocomposite films. PMMA (0.2 g)/ZnPc 6 (0.01 g)/(a) Al (5%); (b)
Al (10%); (c) Al (15%).
Moreover, optical microscopy (OM) images of nanocomposite films are shown in Figures 4a and 4b.
Observation of solid surface nanocomposites in an optical microscope can result in some qualitative information
about dispersion. These images showed that the dispersion in nanocomposite film containing 10% Al is better
than that in other nanocomposites.
a
b
c
Figure 4. Optical microscopy image of nanocomposite films of (a) PMMA (0.2 g)/ZnPc 6 (0.01 g)/Al (5%); (b) PMMA
(0.2 g)/ZnPc 6 (0.01 g)/Al (10%); (c) PMMA (0.2 g)/ZnPc 6 (0.01 g)/Al (15%).
The UV-vis spectra of the phthalocyanines 6–10 in DMF are shown in Figure 5. The UV spectra of the
phthalocyanines 6–10 show single intense bands at λmax = 681, 677, 683, 673, and 682 nm, respectively. There
is also a shoulder-like absorption at slightly higher energy for all the phthalocyanines. The weaker absorptions
appear at 613, 614, 615, 606, and 614 nm for phthalocyanines 6–10, respectively. This is typical of metal
complexes of substituted and unsubstituted metallophthalocyanines with D4 h symmetry.38 The B bands for
6–10 were observed at 334, 333, 350, 333, and 356 nm, respectively (Figure 5; Table 3).
Table 3. Absorption data for phthalocyanines 6–10 in DMF (c = 3 × 10−5 M).
Pc λmax (nm) (log ε)
6
7
8
9
681 (3.83), 613 (3.23), 334 (4.66)
677 (4.45), 613 (3.98), 333 (4.26)
683 (4.97), 615 (4.33), 350 (4.85)
673 (4.84), 606 (4.29), 333 (4.56)
10 682 (4.57), 614 (3.85), 356 (4.28)
Phthalocyanines 6–10 are soluble in THF, CH2 Cl2 , CH3 Cl, DMSO, and DMF. In the solid state, the
absorption spectra for thin films (Figure 6) are different from their solution spectra in which the Q-band looks
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like very sharp. The optical absorption spectra of PMMA/Zn-Pc nanocomposite films for compound 6 shown
in Figure 6 and Table 4 indicate red shifting in the Q-band.
Figure 5. Absorption spectra of 6–10 in DMF (c = 3 ×
Figure 6. Absorption spectra of phthalocyanine 6 in
nanocomposite films (a) PMMA (0.2 g)/ZnPc 6 (0.01 g)/
Al (5%); (b) PMMA (0.2 g)/ZnPc 6 (0.01 g)/Al (10%);
(c) PMMA (0.2 g)/ZnPc 6 (0.01 g)/Al (15%).
10−5 M).
Table 4. Absorption data for phthalocyanine 6 in nanocomposite films.
PMMA/ZnPc/Al λmax Q-band (nm) Al%
a
b
c
685
700
686
5
10
15
PMMA (0.2 g), ZnPc (0.01 g).
The absorption spectra of PMMA/ZnPc/Al nanocomposite films shown clearly demonstrate the absorp-
tion peaks at 600–700 nm corresponding to the Q-bands of phthalocyanine. When compared with the UV/vis
absorption spectrum of ZnPc 6 in DMF, whose main absorption bands are located at 681 and 613 (Q-band)
and 334 nm (B-band), respectively, formation of PMMA/ZnPc/Al nanocomposite films leads to a red shift of
the Q-band.
Aggregation is usually depicted as a coplanar association and is dependent on the nature of solvent,
concentration, nature of substituent, center metal ions, and temperature.39 In the present study the aggregation
behavior of complexes was investigated at different concentration and different solvents. The aggregation
behaviors of phthalocyanines 6–10 at three concentrations (5 × 10−5 , 4 × 10−5 , 3 × 10−5 M) in DMSO,
DMF, CH3 Cl, and THF were considered. The intensity of the absorption bands was increased with increasing
concentration and there were no new bands due to the aggregated species. Thus phthalocyanines 6–10 did
not show aggregation in these solvents at different concentrations. For example, phthalocyanine 6 did not
show aggregation in DMSO. The Lambert–Beer law was obeyed for phthalocyanine 6 as an example in the
concentrations ranging from 5 × 10−5 to 3 × 10−5 M in DMSO (Figure 7).
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Figure 7. Absorption spectra of 6 in DMSO in different concentrations.
Calculations were performed with the Gaussian 0340 system of codes at the restricted Hartree–Fock level
of theory with the 3-21G* basis set.41 The total energies and relative energy of the optimized structures and
dipole moments calculated at HF are presented in Table 5. The results of calculations show that phthalocyanine
6 is more stable than phthalocyanine 10 in the gas phase but the dipole moment of 10 is more than that of
phthalocyanine 6. The optimized molecular structures of phthalocyanines 6 and 10 are shown in Figure 8.
Table 5. The total energy, ratio of energy, dipole moment of 6 and 10 calculated by HF/3-21 G* method.
Pc energya
µbtota
6
–8116.54216342 4.7580
10 –8116.54080792 7.6970
a Total energy in hartree units. b Total dipole moment in debyes.
Figure 8. Optimized geometries of 6 and 10.
The comparative optimized structural parameters such as bond lengths, bond angles, and dihedral angle
values for phthalocyanines 6 and 10 are presented in Table 6. The N1–C2, N3–C4, C4–C5, C2–C10, O11–C12,
C15–C18, and C18–C19 bond lengths were increased but for C7–O11 a reduction in bond length was obtained.
The optimized structure may be compared with the other structures.
3. Experimental
3.1. General
Synthesis of 4-(4-formylphenoxy)phthalonitrile (3a): A mixture of 4-nitrophthalonitrile 1 (1 mmol), 4-hydroxy-
benzaldehyde 2a (1 mmol), and K2 CO3 (1 mmol) was dissolved in 2 mL of DMF. The mixture was stirred at
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room temperature for 24 h. After completion of the reaction, 5 mL of acetone and 4 mL of water were added
consecutively to the reaction mixture and the resulting precipitates were separated and washed with 10 mL of
hot water and 10 mL of ethanol. Yield: 90%, mp: 154 ◦ C. IR vmax /cm−1 (KBr pellet): 3103, 3078 (CHarom),
2850, 2760 (C–Haldehyde), 2236 (C≡N), 1691 (C=O), 1589 (C=C), 1087 (C–O).35
◦
◦
˚
Table 6. Selected optimized bond lengths (A), bond angles ( C), and dihedral angles ( C) of 6 and 10.
Pc Bond lengths
Bond angle
◦C
Dihedral angle
◦C
˚
A
6
N1–C2
N3–C4
C4–C5
C2–C10
C7–O11
O11–C12
C15–C18
C18–C19
1.28 N1–C2–N3
1.33 N3–C4–C5
1.46 N3–C2–C10
1.46 C2–C10–C9
1.39 C4–C5–C6
1.39 C7–O11–C12
1.53 C15–C18–C19 109.75
1.43 C18–C19–C20 122.27
C19–C20–C21 122.98
126.58 N1–C2–C10–C9
109.85 C7–O11–C12–C13
107.49 C7–O11–C12–C17
131.56 C14–C15–C18–C19
132.22 C19–C20–C21–C22
122.43
0.6649
–85.16
101.11
–61.24
179.45
10 N1–C2
N3–C4
C4–C5
1.29 N1–C2–N3
1.36 N3–C4–C5
1.47 N3–C2–C10
1.47 C2–C10–C9
1.38 C4–C5–C6
1.40 C7–O11–C13
1.53 C15–C18–C19 111.05
1.53 C18–C19–C20 121.81
C19–C20–C21 122.88
126.25 N1–C2–C10–C9
108.83 C7–O11–C13–C14
109.15 C7–O11–C13–C12
132.62 C14–C15–CC18–C19 119.62
132.58 C19–C20–C21–C22
129.80
0.8386
31.44
136.70
C2–C10
C7–O11
O11–C13
C15–C18
C18–C19
179.67
Synthesis of (4-(14H-dibenzo[a,j]xanthen-14-yl)phenoxy)phthalonitriles (5a–c): Phthalonitriles 5a–c were
prepared according to our published procedure.42
Synthesis of 2, 9, 16, 23-tetrakis(4-(14H-dibenzo[a,j]xanthen-14-yl)phenoxy)zinc(II) phthalocyanine (6):
A mixture of compound 5a (0.15 g, 0.3 mmol), anhydrous Zn(OAc)2 (0.019 g, 0.1 mmol), DBU (3 drops), and
DMAE (10 mL) was refluxed under nitrogen atmosphere for 18 h. The reaction mixture was then cooled to room
temperature. In the next step ethanol was added and the product was filtered under reduced pressure. The
green solid was washed several times with hot ethanol. This compound was soluble in DMSO, THF, CH3 Cl,
CH2 Cl2 , and DMF. IR vmax /cm−1 (KBr pellet): 3057 (CHarom), 1616 (C=N), 1593 (C=C), 1170, 1087 (C–
O).; 1 H NMR (300 MHz, DMSO-d6) δH : 6.76 (s, 4H, CH), 6.88–7.12 (m, 16H, Ar–H), 7.15–7.65 (m, 32H,
Ar-H), 7.85–7.95 (m, 20H, Ar–H), 8.65–8.75 (m, 8H, Ar–H). (MALDI–TOF) m/z: 2067.57 [M+ ]. Elemental
analysis: calcd (%) for C140 H80 N8 O8 Zn, C 81.59, H 3.91, N 5.44; found, C 81.25, H 4.02, N 5.31.
Synthesis of 2, 9, 16, 23-tetrakis(4-(14H-dibenzo[a,j]xanthen-14-yl)phenoxy)nickel(II) phthalocyanine (7):
A mixture of compound 5a (0.15 g, 0.3 mmol), NiCl2 (0.013 g, 0.1 mmol), three drops of DBU, and DMAE (7
mL) was refluxed at 130 ◦ C under nitrogen atmosphere for 18 h. After cooling to room temperature the mixture
was treated with EtOH (2 mL) in order to precipitate the product. The precipitated dark green product was
filtered off and washed with 10 mL of hot ethanol and 10 mL of hot water. Yield: 38%. IR vmax /cm−1 (KBr
pellet): 3055 (CHarom), 1618 (C=N), 1593, 1502 (C=C), 1165, 1091 (C–O). MS (MALDI–TOF) m/z: 2060.88
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[M+ ]. Elemental analysis: calcd (%) for C140 H80 N8 O8 Ni, C 81.59, H 3.91, N 5.44; found, C 80.95, H 5.25, N
5.61.
Synthesis of 2, 9, 16, 23-tetrakis(4-(14H-dibenzo[a,j]xanthen-14-yl)-2-methoxyphenoxy)zinc (II) phthalo-
cyanine (8): The zinc(II) phthalocyanine 8 prepared as described for 6 using compound 5b (0.16 g, 0.3 mmol),
anhydrous Zn(OAc)2 (0.019 g, 0.1 mmol), and DBU (3 drops) in 10 mL of DMAE. This compound was soluble
in DMSO, THF, CH3 Cl, CH2 Cl2 , and DMF. IR vmax /cm−1 (KBr pellet): 3045 (CHarom), 1616 (C=N), 1593,
1506 (C=C), 1124, 1087 (C–O); 1 H NMR (300 MHz, CDCl3) δH : 3.57 (s, 12H), 6.56 (s, 4H), 6.87–7.91 (m,
64H, Ar–H), 8.41 (d, J = 9.0 Hz, 8H, Ar–H). MS (MALDI–TOF) m/z: 2188 [M+ ]. Elemental analysis: calcd
(%) for C144 H88 N8 O12 Zn, C 79.30, H 4.07, N 5.14; found, C 78.25, H 4.25, N 5.21.
Synthesis of 2, 9, 16, 23-tetrakis(4-(14H-dibenzo[a,j]xanthen-14-yl)-2-methoxyphenoxy)phthalocyanine
nickel(II) phthalocyanine (9): A mixture of compound 5b (0.16 g, 0.3 mmol), NiCl2 (0.013 g, 0.1 mmol), three
drops of DBU, and DMAE (7 mL) was refluxed at 130 ◦ C under nitrogen atmosphere for 18 h. After cooling
to room temperature the mixture was treated with EtOH (2 mL) in order to precipitate the product. The
precipitated dark green product was filtered off and washed with 10 mL of hot ethanol and 10 mL of hot water.
Yield: 41%. IR vmax /cm−1 (KBr pellet): 3031 (CHarom), 1618 (C=N), 1593, 1506 (C=C), 1124, 1093 (C–O);
1 H NMR (300 MHz, CDCl3) δH : 3.59 (s, 12H, CH3), 5.59 (s, 4H, CH), 6.90–6.94 (m, 8H, Ar–H), 7.07–7.13 (m,
8H, Ar–H), 7.21–7.56 (m, 20H, Ar–H), 7.63–7.69 (m, 12H, Ar–H), 7.87–7.93 (m, 16H, Ar–H), 8.42 (d, J = 9
Hz, 8H, Ar–H). MS (MALDI–TOF) m/z: 2180.98 [M+ ]. Elemental analysis: calcd (%) for C144 H88 N8 O12 Ni,
C 79.30, H 4.07, N 5.14; found, C 79.28, H 4.00, N 5.01.
Synthesis of 2, 9, 16, 23-tetrakis(3-(14H-dibenzo[a,j]xanthen-14-yl)phenoxy)zinc(II) phthalocyanine (10):
A mixture of compound 5c (0.15 g, 0.3 mmol), Zn(OAc)2 (0.019 g, 0.1 mmol), three drops of DBU, and
DMAE (7 mL) was refluxed at 130 ◦ C under nitrogen atmosphere for 18 h. After cooling to room temperature
the mixture was treated with EtOH (2 mL) in order to precipitate the product. The precipitated dark green
product was filtered off and washed with 10 mL of hot ethanol and 10 mL of hot water. Yield: 35%. IR
vmax /cm−1 (KBr pellet): 3081 (CHarom), 1618 (C=N), 1593, 1506 (C=C), 1124, 1093 (C–O); 1 H NMR (300
MHz, CDCl3) δH : 6.51–6.73 (m, 8H, Ar–H), 6.93–7.18 (m, 8H, Ar–H), 7.29–7.60 (m, 28H, Ar–H), 7.61–7.69
(m, 20H, Ar–H), 7.80–7.83 (m, 8H, Ar–H), 8.34–8.43 (m, 8H, Ar–H). MS (MALDI–TOF) m/z: 2067 [M+ ].
Elemental analysis: calcd (%) for C140 H80 N8 O8 Zn, C 81.59, H 3.91, N 5.44; found, C 82.00, H 3.98, N 5.12.
Preparation of PMMA/ZnPc film and PMMA/ZnPc/Al nanocomposite films: For the fabrication of the
ZnPc/nanocomposite films, 0.01 g of phthalocyanine 6 was dissolved in 1 mL of DMF. The solution was stirred
at 100 ◦ C for 2 h. Then a solution of 0.2 g of PMMA in 3 mL of DMF was prepared. Both solutions were mixed
together and homogenized by magnetic agitation for 24 h at room temperature. Then the solution was mixed
with three different amounts (0.01, 0.02, and 0.03 g) of aluminum nanoparticles under ultrasound irradiation
for 2 h. Nanocomposite films were cast by pouring the solutions of each concentration into petri dishes placed
on a leveled surface followed by evaporation of the solvent at 70 ◦ C over 12 h. The films were dried at 80 ◦ C
for 24 h under vacuum to a constant weight. The mixture was poured in petri dishes and placed on a leveled
surface.
4. Conclusion
Tetra-substituted metallophthalocyanines 6–10 bearing dibenzoxanthenes have been synthesized for the first
time in good yield. These complexes have been characterized on the basis of their elemental analysis and by
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UV-vis, FT-IR, 1 H NMR, and MALDI–TOF mass spectroscopies and thermogravimetric analysis. Moreover,
metallophthalocyanine 6 has been incorporated into polymer PMMA host and nanocomposite films by varying
the amounts of Al from 5% to 15% were synthesized. The obtained solid nanocomposites exhibit red shifting in
the Q-band. Among the produced nanocomposite thin films, nanocomposite film containing 10% Al showed the
most red shift in Q-band absorption. The structure and morphology of PMMA/ZnPc/Al nanocomposite films
were studied using XRD, SEM, and OM. The average size of nanocomposite film containing 10% Al was 29.8
nm. Geometry optimization of two complexes at RH/3-21G* computational level gives more insights regarding
structural parameters in studied complexes.
Acknowledgment
We gratefully acknowledge the financial support from the Research Council of Arak University.
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