Accepted Manuscript

Research paper

Comparative nonlinear optics and optical limiting properties of metallophtha-

locyanines

Zekeriya Biyiklioglu, Tayfun Arslan, Fadheela A. Alawainati, Hacene Manaa,

Adnan Jaffar, Fryad Z. Henari

PII: S0020-1693(18)31233-7
DOI: https://doi.org/10.1016/j.ica.2018.10.061
Reference: ICA 18607

To appear in: Inorganica Chimica Acta

Received Date: 7 August 2018

Revised Date: 26 September 2018
Accepted Date: 27 October 2018

Please cite this article as: Z. Biyiklioglu, T. Arslan, F.A. Alawainati, H. Manaa, A. Jaffar, F.Z. Henari, Comparative
nonlinear optics and optical limiting properties of metallophthalocyanines, Inorganica Chimica Acta (2018), doi:
https://doi.org/10.1016/j.ica.2018.10.061

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 Comparative nonlinear optics and optical limiting properties of
metallophthalocyanines

Zekeriya Biyiklioglu1*, Tayfun Arslan2,3, Fadheela A. Alawainati4, Hacene

Manaa4, Adnan Jaffar4, Fryad Z. Henari5

1
Karadeniz Technical University, Department of Chemistry, Trabzon, 61080, Turkey
2
Giresun University, Department of Chemistry, 28200, Giresun, Turkey.
3
Giresun University, Technical Sciences Vocational School, 28049, Giresun, Turkey.
4
University of Bahrain,Department of Physics, P.O.Box 32038, Kingdom of Bahrain.
5
Medical University of Bahrain,Department of Medical Sciences, Kingdom of Bahrain.

Abstract

In this study, peripherally tetra-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted cobalt(II),
manganese(III), copper(II) phthalocyanines 2a-2c and axially di-{2-[[4-((E)-{[4-
(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted silicon
phthalocyanine 3 were synthesized for the first time. These compounds were characterized by
standard spectroscopy methods. Their nonlinear optical properties are evaluated with the help
of z-scan technique. Both open and closed aperture configurations show clear z-scan signal in
the four samples. The refractive nonlinear index n2 is found to be ranging between -4.9 and -
28.1 x 10-8 cm2/W, and the nonlinear absorptive coefficient varied between 0.2 and 5.4 x 10-3
cm/W. The optical limiting measurements showed low threshold levels, 645 W/cm2 in 2c and
680 W/cm2 in 2a in full agreement with Z-scan measurements.

Keywords: Synthesis; Phthalocyanine; Silicon; Z-scan; Optical limiting; Nonlinear optics

Corresponding author; Tel: +90 462 377 36 64, Fax:+90 462 325 31 96
E-mail address: [email protected] (Z. Bıyıklıoğlu)

1
1. Introduction

The area of nonlinear optics (NLO) has been developing for a few decades as a

promising field with considerable applications in the domain of photoelectronics and

photonics. Organic compounds possessing highly delocalized π-electron systems have been

used for nonlinear optical applications [1]. Nonlinear optical (NLO) materials play a major

role in nonlinear optics and in particular they have a great impact on information technology

and industrial applications [2]. Among the wide variety of NLO organic materials

investigated, phthalocyanines (Pcs) and other related compounds have attracted much interest

in this field [3].

Phthalocyanine molecules with a two-dimensional conjugated π -electrons system

provides a large charge transfer [4-6]. Because of these properties, Pcs and their derivatives

have been used widespreadly in different technological areas such as gas and chemical

sensors, electrochromic and electroluminescent displays, nonlinear optics, photovoltaics,

optical switching and optical limiting and so forth [7-11]. These aromatic macrocyclic

compounds are one of the most attractive macrocycle systems for third-order nonlinear optical

(NLO) response due to their exceptional thermal and chemical stability properties [3].

In particular, phthalocyanines have been intensively investigated because these

molecules offer the advantage of large nonlinear optical susceptibilities and enormous

architectural flexibility that can be easily modified by organic chemists [12]. Phthalocyanines

and analogues can alter the electronic structure of the macrocyclic core, and therefore, they

allow the fine-tuning of the nonlinear response. Furthermore, the high stability and capability

of phthalocyanines to accommodate different metallic ions in their cavity result in the diverse

optical properties [13].

2
 In this study, we have synthesized cobalt(II), manganese(III), copper(II)

phthalocyanines bearing {2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}groups on peripheral

position. Also, we have synthesized axially disubstituted silicon phthalocyanine. All

phthalocyanines were characterized by various spectroscopic techniques. In addition, we have

investigated nonlinear optical properties of metallophthalocyanines (M = Co, Cu, Mn, Si).

2. Experimental

2.1. Materials and equipments

All reagents and solvents were of reagent grade quality and were obtained from

commercial suppliers. All solvents were dried and purified as described by Perrin and

Armarego [14]. The IR spectra were recorded on a Perkin Elmer 1600 FT-IR

Spectrophotometer, using KBr pellets. 1H and 13

C-NMR spectra were recorded on a Bruker

Avance III 400 MHz spectrometers in CDCl3, DMSO-d6 and chemical shifts were reported ()

relative to Me4Si as internal standard. MALDI-MS of complexes were obtained in

dihydroxybenzoic acid as MALDI matrix using nitrogen laser accumulating 50 laser shots

using Bruker Microflex LT MALDI-TOF mass spectrometer Bremen, Germany). The UV-Vis

absorption spectra were recorded on Perkin Elmer Lambda 25 UV-Vis spectrophotometer at

room temperature. The elemental analyses were performed on a Costech ECS 4010

instrument.

2.2. Synthesis

2.2.1. (E)-2-((4-((4-(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethanol (1)

3
A mixture of 4-((2-hydroxyethyl)(methyl)amino)benzaldehyde (1 g, 5.6 mmol), N,N-

dimethyl-p-phenylenediamine (0.760 g, 5.6 mmol) and four drops of acetic acid were added

to ethanol (0.06 L) in a two-necked round-bottom flask equipped with a reflux condenser. The

reaction mixture was stirred in an oil bath at 85 °C under a nitrogen atmosphere. After stirring

for 1 day, the solvent was evaporated under reduced pressure to near dryness. The crude

product was purified by recrystallization from ethanol. Yield: 1.60 g (96%). IR (ATR) ν (cm-
1
): 3176 (-OH), 3044 (Ar-H), 2862-2831 (Aliph. C-H), 1603, 1522, 1353, 1176, 1070, 820,

807. 1H-NMR (400 MHz, DMSO-d6), (δ:ppm): 8.40 (s, 1H, =CH-), 7.70 (d, 2H, J= 8.8, Ar-

H), 7.17 (d, 2H, J= 8.8, Ar-H), 6.77 (d, 2H, J= 9.2, Ar-H), 6.74 (d, 2H, J= 9.4, Ar-H), 4.75 (s,

1H, -OH), 3.60 (t, 2H, J= 12, -CH2-O), 3.48 (t, 2H, J= 12, -CH2-N), 3.01 (s, 3H, N-CH3),

2.90 (s, 6H, -CH3). 13

C-NMR (100 MHz, DMSO-d6), (δ:ppm): 155.89, 151.36, 149.07,

141.65, 130.13, 124.70, 122.23, 113.35, 111.65, 58.59, 54.45, 40.85, 39.18. MS (ESI), (m/z)

calcl. 297.39; found: 298.23 [M+H]+. Elemental Analysis: (Found: C 72.86, H 7.65, N

14.29%, C18H23N3O (297.39) requires C 72.70, H 7.80, N 14.13%).

2.2.2. (E)-4-(2-((4-((4-(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethoxy)

phthalonitrile (2)

(E)-2-((4-((4-(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethanol (1) (1 g,

3.37 mmol), 4-nitrophthalonitrile (583.5 mg, 3.37 mmol) and K2CO3 (1.40 g, 10.10 mmol) in

dry DMF (20 mL) were stirred at 50C for 4 days under a nitrogen atmosphere. Then, reaction

mixture was poured into water. After filtration under vacuum, the crude product was

crystallized from ethanol. Yield: 0.79 g (56%), m.p: 173-174 ºC. IR (ATR) ν (cm-1): 3072

(Ar-H), 2887-2858 (Aliph. C-H), 2233 (CN), 1604, 1520, 1347, 1184, 1174, 821, 809. 1H-

NMR (400 MHz, DMSO-d6), (δ:ppm): 8.42 (s, 1H, =CH-), 8.03 (d, 1H, J= 8, Ar-H), 7.76 (d,

1H, J= 8, Ar-H), 7.71 (d, 2H, J= 8, Ar-H), 7.44 (dd, 1H, J= 7.9, Ar-H), 7.17 (d, 2H, J= 8, Ar-

4
H), 6.83 (d, 2H, J= 8, Ar-H), 6.74 (d, 2H, J= 8, Ar-H), 4.34 (t, 2H, J= 10, -CH2-O), 3.85 (t,

2H, J= 10, -CH2-N), 3.05 (s, 3H, N-CH3), 2.90 (s, 6H, -CH3). 13C-NMR (100 MHz, DMSO-

d6), (δ:ppm): 162.18, 155.81, 150.96, 149.15, 141.51, 136.20, 130.12, 125.38, 122.27, 120.79,

120.55, 116.75, 116.66, 116.15, 113.32, 112.05, 106.51, 67.22, 50.77, 40.84, 39.16. MS

(ESI), (m/z) calcl. 423.50; found: 424.78 [M+H]+. Elemental Analysis: (Found: C 73.90, H

5.79, N 16.29%, C26H25N5O (423.50) requires C 73.74, H 5.95, N 16.54%).

2.2.3. 2(3),9(10),16(17),23(24)-Tetrakis-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}phthalocyaninato

cobalt(II) (2a)

(E)-4-(2-((4-((4-(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethoxy)

phthalonitrile 2 (150 mg, 0.35 mmol), CoCl2 (22 mg, 0.17 mmol), n-pentanol (2 mL) and 1,8-

diazabycyclo[5.4.0]undec-7-ene (DBU) (4 drops) was immersed into oil bath preheated to

160C and stirred at this temperature for 24 h under a nitrogen atmosphere. The solution was

poured into hexane. The precipitate was filtered off and crude product was purified by column

chromatography on aluminum oxide by using CHCl3 as solvent. Yield: 36 mg (24%), m.p. 

300 ºC. IR (ATR) ν (cm-1): 3037 (Ar-H), 2923-2878 (Aliph. C-H), 1604, 1518, 1456, 1376,

1343, 1278, 1226, 1170, 1120, 1062, 814, 751. UV-Vis (CHCl3) λmax nm (log ): 674 (4.45),

634 (4.13), 379 (4.88), 331 (4.94). MALDI-TOF-MS m/z calc. 1752.97; found: 1752.43 [M]+.

Elemental Analysis: (Found: C 71.44, H 5.56, N 16.20%, C104H100N20O4Co (1752.97)

requires C 71.26, H 5.75, N 15.98%).

2.2.4. 2(3),9(10),16(17),23(24)-Tetrakis-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}phthalocyaninato

manganese(III) (2b)

5
2(3),9(10),16(17),23(24)-Tetrakis-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}phthalocyaninato

manganese(III) (2b) was synthesized similarly to 2a by using anhydrous MnCl2 instead of

anhydrous CoCl2. Yield: 36 mg (23%), m.p.  300 ºC. IR (ATR) ν (cm-1): 3044 (Ar-H), 2923-

2868 (Aliph. C-H), 1591, 1520, 1509, 1454, 1338, 1228, 1167, 1118, 1074, 1056, 812, 743,

729. UV-Vis (CHCl3) λmax nm (log ): 731 (4.78), 656 (4.26), 526 (4.06), 385 (4.86), 336

(4.95). MALDI-TOF-MS m/z calc. 1784.42; found: 1748.21 [M-Cl]+. Elemental Analysis:

(Found: C 70.25, H 5.41, N 15.92%, C104H100N20O4MnCl (1784.42) requires C 70.00, H 5.65,

N 15.70%).

2.2.5. 2(3),9(10),16(17),23(24)-Tetrakis-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}phthalocyaninato

copper(II) (2c)

2(3),9(10),16(17),23(24)-Tetrakis-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}phthalocyaninato

copper(II) (2c) was synthesized similarly to 2a by using anhydrous CuCl2 instead of

anhydrous CoCl2. Yield: 27 mg (18%), m.p.  300 ºC. IR (ATR) ν (cm-1): 3037 (Ar-H), 2919-

2850 (Aliph. C-H), 1604, 1509, 1479, 1342, 1228, 1172, 1117, 1094, 1057, 813, 745. UV-Vis

(CHCl3) λmax nm (log ): 683 (4.83), 618 (4.57), 378 (5.09), 337 (5.08). MALDI-TOF-MS m/z

calc. 1757.58; found: 1757.07 [M]+. Elemental Analysis: (Found: C 71.38, H 5.60, N 16.19%,

C104H100N20O4Cu (1757.58) requires C 71.07, H 5.73, N 15.94%).

6
2.2.6. Bis-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}phthalocyaninatosilico

n(IV) (3)

A mixture of SiPcCl2 (71 mg, 0.11 mmol) and (E)-2-((4-((4-

(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethanol (69 mg, 0.23 mmol) in

toluene (15 mL) was stirred and then sodium hydride (5.5 mg, 0.23 mmol) was added to this

mixture. After heating at reflux temperature under nitrogen atmosphere for 24 h, toluene was

evaporated to dry under reduced pressure. The green product was purified by column

chromatography [aluminum oxide, CHCl3]. Yield: 91 mg (70%), m.p.  300 ºC. IR (ATR) ν

(cm-1): 3037 (Ar-H), 2962-2830 (Aliph. C-H), 1591, 1509, 1426, 1333, 1259, 1101, 1077,

1015, 908, 795, 731. 1H-NMR (400 MHz, CDCl3), (δ): 9.53 (m, 8H, Pc-Hα), 8.33 (m, 8H, Pc-

H), 8.03 (s, 2H, =C-H), 7.38 (m, 2H, Ar-H), 7.21-7.19 (m, 4H, Ar-H), 6.94 (m, 2H, Ar-H),

6.79.6.77 (m, 4H, Ar-H), 4.81 (m, 4H, Ar-H), 3.08 (s, 12H, CH3), 0.88 (s, 6H, N-CH3), 0.55

(m, 4H, CH2-N), -1.96 (m, 4H, Si-O-CH2). 13C-NMR (100 MHz, CDCl3), (δ): 149.17, 135.76,

135.70, 135.65, 130.92, 130.82, 130.73, 129.04, 128.23, 123.67, 121.89, 113.46, 109.18,

51.82, 50.77, 41.10, 35.97. UV-Vis (CHCl3) λmax nm (log ): 678 (4.90), 651 (4.23), 610

(4.22), 355 (4.72). MALDI-TOF-MS m/z calc. 1133.38; found: 1133.40 [M]+. Elemental

Analysis: (Found: C 72.24, H 5.16, N 17.47%, C68H60N14O2Si (1133.38) requires C 72.06, H

5.34, N 17.30%).

2.3. Z-scan technique:

Z-scan technique was used to investigate the nonlinear optical properties of the four-

phthalocyanine compounds. This experimental technique permits to separately evaluate the

refractive and absorptive nonlinear parameters [15]. It relies on the fact that the intensity of

7
the incident laser beam varies along the optical axis of a convex lens and it reaches its

maximum at the lens’s focus. The sample can be displaced along the z-axis by a computer-

controlled motorized translational stage with a resolution of 0.05 mm. More details about our

experimental z-scan setup can be found in [16].

The z-scan method is based on the measurements of the samples’ transmittance in two

different configurations: In the first one, an aperture is installed at the entrance of the detector

(closed aperture), whereas in the second case, the whole beam falls on the detector (open

aperture). The closed case gives the information about the nonlinear refractive index while the

open one gives information on the nonlinear absorption coefficient.

In the open aperture configuration, the sample’s normalized transmittance is given by [15]:

(1)

Where x =z/z0 and z0 = π /λ is the diffraction length of the Gaussian beam, ω 0 is the beam

waist and is the nonlinear phase change parameters that is related to the nonlinear

absorption coefficient β by:

(2)

Where is the linear absorption coefficient ( = Absorbance x ln(10)/l), l is the thickness of

the sample and I0 is the peak laser irradiance at the focus ( ) where P is the laser

power. A fit of Equation (1) to the experimental data is used to calculate the values of

nonlinear absorption at 632.8 nm for all the samples. The results are shown in Table 1.

The nonlinear absorption coefficient  is related to the imaginary part of the third order

nonlinear susceptibility through:

(3)

Where n is the index of refraction, is the free space permittivity, and c is the speed of light.

8
In the case of closed aperture configuration, the normalized transmittance is given by [15]:

(4)

Where is the laser-induced phase shift that is related to the nonlinear refractive coefficient

n2 by the equation:

(5)

The nonlinear refractive index was obtained by the fitting of Equation (4) to the experimental

data. The refractive nonlinear coefficient is related to the real part of the third order

susceptibility through:

(6)

From Eq. 3 and Eq. 6, the absolute value of is then given by:

(7)

3. Results and discussion

3.1. Synthesis and Characterization

General synthetic route for the synthesis of compounds 1, 2, 2a, 2b, 2c, are given in Figure 1.

Firstly, 4-((2-hydroxyethyl)(methyl)amino)benzaldehyde was treated with the N,N-dimethyl-

p-phenylenediamine in ethanol in the presence of a few drops of acetic acid led to compound

1. Then, the phthalonitrile derivative 2 was obtained by the aromatic nucleophilic substitution

reaction of (E)-2-((4-((4-(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethanol

with 4-nitrophthalonitrile. The cyclotetramerization of the phthalonitrile derivative 2 in the

9
presence of anhydrous CoCl2, MnCl2 and CuCl2 in n-pentanol and a few drops DBU as a

strong base at reflux temperature under a nitrogen atmosphere afforded the peripherally tetra-

{2-[[4-((E)-{[4-(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}

substituted cobalt(II), manganese(III), copper(II) phthalocyanines (2a, 2b and 2c). Reaction of

silicon(IV) phthalocyanine dichloride with (E)-2-((4-((4-

(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethanol 1 in the present of NaH

in toluene led to the target axially disubstituted silicon(IV) phthalocyanine 3.

In the IR spectra, the formation of compound 1 was clearly confirmed by the

disappearance of the NH2 and the C=O bands and by the appearance of the OH and the HC=N

bands at 3176 and 1603 cm−1 respectively. The 1H-NMR spectra were also in good agreement

with the structures of compound 1. The molecular ion peak of 1 was found at m/z 298.23 [M

+ H]+. In the IR spectrum of (E)-4-(2-((4-((4-

(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethoxy)phthalonitrile 2, the

absorption band at 2233 cm-1 was assigned to the CN stretching. In 1H NMR spectrum of 2,

the disappearance of the OH peaks of (E)-2-((4-((4-

(dimethylamino)phenylimino)methyl)phenyl)(methyl)amino)ethanol 1, besides presence of

additional aromatic protons indicated that nucleophilic aromatic nitro displacement was

achieved. Also, the molecular ion peak of 2 was found at m/z 424.78 [M+H]+. The absence of

the intense nitrile stretches at 2233 cm-1 (compound 2) in the infrared spectra of the metal

complexes affirms that the cyclotetramerization reactions occurred. Also, the formation of

bis-{2-[[4-((E)-{[4-(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy}

phthalocyaninatosilicon(IV) 3 was clearly confirmed by the disappearance of the OH bands at

3176 cm-1 for 1 in the IR spectrum of silicon phthalocyanine 3. 1H-NMR and 13

C-NMR

measurements of the cobalt(II) manganese(III) and copper(II) phthalocyanines 2a, 2b, 2c

were precluded due to their paramagnetic nature [17]. In the 1H NMR spectra of silicon

10
phthalocyanine 3, the phthalocyanine ring proton resonances appeared as multiplets

integrating each as 8H at (9.53)-(8.33) ppm, for the α and β protons, respectively. Because of

magnetic anisotropy of phthalocyanine ring [18], the peaks belonging to aliphatic CH2

protons in Si-O-CH2 bond were shifted toward the negative region (-1.96 ppm). In the

MALDI-TOF mass spectrum of peripherally tetra-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted cobalt(II),

manganese(III), copper(II) phthalocyanines 2a-2c and axially di-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted silicon

phthalocyanine 3 the molecular ion peaks were observed at 1752.43 [M]+ (Figure 2a), 1748.21

[M-Cl]+, 1757.07 [M]+ (Figure 2b), 1133.40 [M]+, respectively. The UV-Vis absorption

spectrum of 2a, 2b, 2c, 3 in CHCl3 was shown in Figure 3. The peripherally tetra-{2-[[4-((E)-

{[4-(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted

cobalt(II), manganese(III), copper(II) phthalocyanines 2a-2c and axially di-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted silicon

phthalocyanine 3, showed the expected absorptions of the Q bands at 674, 731, 683, 678 nm

and B bands at (379, 331), (385, 336), (378, 337), 355 nm, respectively.

3.2 Nonlinear optical properties:

In our Z- scan experiments was we used a HeNe laser (632.8 nm, power 10 mW). A lens of

50 mm focal length was used to focus the laser beam to a roughly 20 m beam waist. The

compounds were dissolved in dimethylformamide (DMF) with a concentration of 4.5 x 10 -5

M. Our findings reveal that both the nonlinear refractive and absorptive effects are present in

the four samples. Figure 4 shows the open aperture Z-scan signal for 2a along with the fitting

of the experimental data with Eq. 1. The sample’s transmittance strongly decreases at the

focus (z = 0). A nonlinear absorption coefficient  is found to be 2.3 x 10 -3 cm/W. As shown

11
in Table 1, the absorptive nonlinear effect clearly varies from one sample to the other. It

increases from 0.2 x 10-3 cm/W in 2b to 5.4 x 10-3 cm/W in 2c. These values are of the same

order of magnitude of those found in similar compounds [16].

The positive sign of  is attributed to Reverse Saturation Absorption (RSA), where the

Z-scan signal depends on the difference between the ground state absorption (GSA) and the

excited state absorption (ESA) cross sections, abs-esa.

Figure 5 shows the 2a Z-scan signal for the closed aperture configuration at  = 632.8

nm with the fitting of the experimental data with Eq. 4. The results reveal a strong nonlinear

refractive effect, and the negative sign of the nonlinear refractive index n2 means that the

samples are behaves like divergent lenses. When the sample moves along z-axis, before the

focus, the laser beam experiences a collimation that increases the transmittance. When the

sample is beyond the focus it enhances the divergence of the laser beam and consequently

decreases its transmittance.

For the refractive effects, it is remarkable that our results show the same disparity

between the samples found for the absorptive effects. The largest values of n2 are found in 2a

and 2c.

The origin of these optical large nonlinearities, and by anticipation of the excellent

optical limiting performances that are shown below, is probably due to optical electronic

effects (optical transition and variation of the transitions and population) and thermal effects.

Even though, the low incident powers used in the experiments, there may be a contribution of

the thermal lensing which give the same type of Z-scan signals. The evaluation of the

contribution of each effect can be done by using pulsed lasers along with CW lasers.

3.3. Optical Limiting:

12
It is well known that passive optical limiters, OL, are optical devices that transmit a maximum

of weak light and become opaque for intense light. Either in the case of RSA or TPA, The

absorption of the photons is nonlinear, i.e. once the intensity of the laser beam increases, the

photons start to be more absorbed instead of being transmitted. This is the absorption-based

OL. Another possible mechanism that can make NLO materials contribute to optical

limitation is due to the change of molecular polarization under laser excitation, which leads to

refractive-based optical limiting that operates by increasing the divergence of the solid angle

of the transmitted laser beam at large incident powers [19,20].

Figure 6 shows the optical limiting behavior of our four samples under the excitation

of laser radiation at 632 nm. The transmittance is roughly constant at low irradiance and

obeys the Lambert–Beer law (linear part) but decreases dramatically at large irradiances

(nonlinear part). The optical limiting threshold, defined as the incident laser irradiance when

the sample’s transmittance is 0.5 is found to be 680 W/cm2 in 2a nm, and 635 W/cm2 in 2c.

These OL performances are in full agreement with the values of nonlinear absorption and

nonlinear refraction. The samples with large  and n2 have the lowest

OL thresholds.

Conclusion

As a conclusion, peripherally tetra-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted cobalt(II),

manganese(III), copper(II) phthalocyanines and axially di-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} substituted silicon

phthalocyanine were successfully synthesized. The new compounds were characterized by IR,
1 13
H-NMR, C-NMR, UV-Vis (except compound 1, 2), MS spectroscopic methods and
13
elemental analysis. Z-scan technique used to evaluate the nonlinear optical properties reveals

that the four samples show nonlinear behavior, either in the open or closed aperture

configurations. However, two groups can be distinguished: 2a and 2c show stronger nonlinear

absorptive and refractive parameters than 2b and 3. This result is confirmed by the OL

measurements where the two same samples show a very low OL threshold of 680 W/cm 2 in

Pc2a and 645 W/cm2, meanwhile the two other samples did not reach the OL threshold in our

range of measurements. These OL threshold values are of the same order of magnitude of

those obtained in similar compounds [9]. It is very clear that the metallic substitution with Co

and Cu is more favorable to the nonlinear performance than the MnCl one. On the other

hand, the tetra-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} chemical structure

seems to be giving better nonlinear effects than the di-{2-[[4-((E)-{[4-

(dimethylamino)phenyl]imino}methyl)phenyl](methyl)amino]ethoxy} one. Its worthy to

mention here that in a recent work [21], the Pc compounds without incorporated metal show

better OL performances than those with metal. These result dissimilarities require more

investigations.

Acknowledgements

This study was supported by The Research Fund of Karadeniz Technical University, Trabzon,

Turkey.

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14
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17
Table 1. Nonlinear optical parameters of phthalocyanine components at 632.8 nm.

χ(re), O.L.
α, β, n2 , χ(im), m /V χ (tot),
2 2
Threshold
P, cm- cm/W cm /W m2/V2
2
x 10 - 2
m /V 2
Χ(im)/(χre) W/cm2
1
mw x 10-3 x 10-8 x 10-15 15
x 10-15 %
2a 10.2 0.29 2.3 -28.1 12.3 -281 281 4 680
2b 10.5 0.14 0.2 -4.9 0.9 -49.4 49.4 2 >1500
2c 10.5 0.56 5.4 -17.4 29.5 -174 177 17 645
3 10.5 0.06 0.5 -6.3 2.5 -63 63 4 >1500

18
Figure Captions

Figure 1. The synthesis of metallophthalocyanines 2a-2c and silicon phthalocyanine 3.

Figure 2. (a) MALDI-TOF MS spectrum of cobalt(II) phthalocyanine 2a. (b) MALDI-

TOF MS spectrum of copper(II) phthalocyanine 2c.

Figure 3. The UV-Vis spectrum of 2a, 2b, 2c, 3 in CHCl3. Concentration = 1.00 × 10−5

mol x dm-3.

Figure 4 Open aperture Z-scan signal of 2a at λ=633 nm and P = 10.15 mw.

Figure 5. Closed aperture Z-scan signal of 2a at λ=632.8 nm and P = 10.15 mw.

Figure 6. Optical limiting of 2a (blue star), 2b (red square), 2c (circle) and 3 (full circle).

19
Figure 1.

20
Figure 2.

21
Figure 3.

22
 1.04

1.02

1.00

0.98
Transmittance

0.96

0.94

0.92

0.90

0.88

0.86
-1.0 -0.5 0.0 0.5 1.0 1.5
Z(cm)

Figure 4.

23
 2.0

1.8

1.6

1.4
Transmittance

1.2

1.0

0.8

0.6

0.4

0.2

0.0
-1.0 -0.5 0.0 0.5 1.0 1.5
Z(cm)

Figure 5.

24
 1.2

1.0

0.8
Transmittance

0.6

0.4

0.2

0.0
200 400 600 800 1000
2
Incident Irradiance (W/cm )

Figure 6.

25
Graphical Abstract

1.04 2.0 1.2

1.02 1.8
1.0
1.6
1.00
1.4
0.98 0.8

Transmittance
Transmittance

Transmittance

1.2
0.96
1.0 0.6
0.94
0.8
0.92 0.4
0.6
0.90
0.4
0.2
0.88 0.2

0.86 0.0 0.0

-1.0 -0.5 0.0 0.5 1.0 1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 200 40

Z(cm) Z(cm) Inc

26
►Synthesis of new metallophthalocyanines. ► Synthesis of new silicon phthalocyanine.
►Nonlinear optical properties of phthalocyanines.

27