Synthesis and investigation of spectroelectrochemical properties of peripherally tetra-substituted phthalocyanine bearing 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol and its metallo compounds

Article abstract of DOI:10.1007/s10847-018-0837-6

In this study, the new compounds; 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol 3 was prepared by the reaction of 4-(3-hydroxypropyl)phenol 1 with 1-(bromomethyl)-3-(trifluoromethyl)benzene 2 and 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] phthalonitrile 5 was synthesized by the reaction of 4-nitrophthalonitrile 4 with 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol 3. Novel peripherally tetra substituted H₂Pc 6, Co(II) 7, Cu(II) 8, Ni(II) 9 and Fe(II) 10 phthalocyanines, which have peripheral positions with 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] groups, were synthesized and all of the new compounds characterized by IR, ¹H NMR, ¹³C NMR, UV–Vis, mass spectroscopies and elemental analysis. The electrochemical and spectroelectrochemical investigation of the phthalocyanines carrying 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] groups were studied using various electrochemical techniques in DMF on a glassy carbon electrode. Cyclic voltammetry and square wave voltammetry studies show that the complexes have either metal based or ligand-based diffusion controlled electron transfer properties. To shed more light on the electron-transfer steps of the complexes and assignments of the redox couples were carried out by spectroelectrochemical measurements. The color changes during spectral changes of redox species were recorded with in situ electrocolorimetric measurements. The electrochemical and in situ UV–Vis spectral change of complexes indicated their applicability in the fields of the electrochemical technologies.

Full text of DOI:10.1007/s10847-018-0837-6

Journal of Inclusion Phenomena and Macrocyclic Chemistry
https://doi.org/10.1007/s10847-018-0837-6
ORIGINAL ARTICLE
Synthesis and investigation of spectroelectrochemical properties
of peripherally tetra-substituted phthalocyanine bearing
3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol and its
metallo compounds
Ayşe Aktaş Kamiloğlu1 · Duygu Akyüz2 · Atıf Koca3 · İrfan Acar4
Received: 10 April 2018 / Accepted: 25 August 2018
© Springer Nature B.V. 2018
Abstract
In this study, the new compounds; 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol 3 was prepared by the reaction
of 4-(3-hydroxypropyl)phenol 1 with 1-(bromomethyl)-3-(trifluoromethyl)benzene 2 and 4-[3-(4-{[3 (trifluoromethyl)benzyl]
oxy}phenyl)propoxy] phthalonitrile 5 was synthesized by the reaction of 4-nitrophthalonitrile 4 with 3-(4-{[3-(trifluorome-
thyl)benzyl]oxy}phenyl)propan-1-ol 3. Novel peripherally tetra substituted H2Pc 6, Co(II) 7, Cu(II) 8, Ni(II) 9 and Fe(II) 10
phthalocyanines, which have peripheral positions with 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] groups,
were synthesized and all of the new compounds characterized by IR, 1H NMR, 13C NMR, UV–Vis, mass spectroscopies and
elemental analysis. The electrochemical and spectroelectrochemical investigation of the phthalocyanines carrying 4-[3-(4-
{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] groups were studied using various electrochemical techniques in DMF on
a glassy carbon electrode. Cyclic voltammetry and square wave voltammetry studies show that the complexes have either
metal based or ligand-based diffusion controlled electron transfer properties. To shed more light on the electron-transfer
steps of the complexes and assignments of the redox couples were carried out by spectroelectrochemical measurements.
The color changes during spectral changes of redox species were recorded with in situ electrocolorimetric measurements.
The electrochemical and in situ UV–Vis spectral change of complexes indicated their applicability in the fields of the elec-
trochemical technologies.
Keywords Phthalocyanine · Synthesis · Electrochemistry · Voltammetry
Introduction
In recent years, phthalocyanines (Pcs) have been generally
studied since they have been applied to many scientific field
applications such as chemical sensors [1], catalysts [2, 3],
photodynamic therapy [4, 5], electrochromic agent [6], dyes
* Ayşe Aktaş Kamiloğlu
and pigments [7], liquid crystal [8], electrocatalytic [9] and
ayse_aktas_kamiloglu@artvin.edu.tr;
solar energy conversion [10].
ayse_aktas@hotmail.com
A major deficiency of the metal-free and metallo Pcs is
1
that their solubility organic solvents is very poor [11]. The
lower solubility of Pcs prevents from their application in
many areas. The solubility of Pcs can be increased by the
affiliation with various alkyl, aryloxy, macrocyclic, alkoxy
and phenoxy groups on the peripheral and non-peripheral
positions.
Artvin Vocational School, Artvin Çoruh University,
08100 Artvin, Turkey
2
3
4
Department of Chemistry, Faculty of Science and Letters,
Marmara University, 34722 Istanbul, Turkey
Department of Chemical Engineering, Engineering Faculty,
Marmara University, 34722 Istanbul, Turkey
Metallophthalocyanines are a member of transition metal
complexes known as macrocyclic complexes. They have an
Department of Energy Systems Engineering, Faculty
of Technology, Karadeniz Technical University,
61830 Trabzon, Turkey
Vol.:(0123456789)
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
inner structure that is common in naturally occurring mol-
ecules such as heme groups in hemoglobin, chlorophyll,
cytochrome c, vitamin B12 [12–14]. The reason why these
molecules are unusual in many areas, besides their strong
absorption in the UV–Vis region and their electrical prop-
erties, Pcs are also thermally and chemically stable com-
pounds, and can support intense electromagnetical radia-
tions [15]. In addition, they have properties such as being
in combination with different metals and various substitu-
ents, thanks to these features can make fine adjustment of
the physical properties [16]. Recently, Pcs have appeared
as charming molecule for their arrangement into molecu-
lar materials and for fabricating materials at the nanometer
scale. Thus, Pcs can be used successfully as active com-
ponents of organic field effect transistors, electrochromic
materials and solar cells, etc [15, 17].
18-crown-6 (0.19 g, 0.73 mmol) was added to this solu-
tion. The reaction mixture was refluxed under nitrogen for
48 h. After the mixture was cooled, the solvent was removed
under vacuum, and the resulting crude product was dissolved
in 70 ml of chloroform (CHCl3). The mixture was washed
with 35 ml of water. The organic phase was dried over mag-
nesium sulphate (MgSO4), filtered and rotary evaporated.
The obtained oily crude product was purified using column
chromatography with basic aluminium oxide as the column
material and a chloroform/methanol (10:2) solvent system.
Yield: 1.72 g (84.72%). IR (KBr tablet), νmax/cm−1: 3371
(Aliph–OH), 3031 (Ar–H), 2933–2868 (Aliph. C–H), 1611
(C=C), 1328, 1119–1072 (C–O–C), 906 (C–H), 798, 698.
1H–NMR. (CDCl3), (δ: ppm): 7.74 (s, 2H, Ar–H), 7.63–7.51
(m, 2H, Ar–H), 7.27 (d, 2H, Ar–H), 6.95 (d, 2H, Ar–H), 5.09
(s, 2H, –O–CH2–Ar), 3.71 (m, 2H, –O–CH2), 3.54 (s, 1H,
The electrochemical properties of Pcs are generally deter-
mined by voltammetric techniques such as cyclic voltam-
metry (CV), differential pulse voltammetry and square-wave
voltammetry (SWV). In addition, the nature of the redox
process can be clarified with the in situ spectroelectrochemi-
cal measurements [18–20].
O–H), 2.70 (t, 2H, –CH2), 1.93 (m, 2H, –CH2) (Fig. 1). 13
C
NMR. (CDCl3), (δ: ppm): 156.73 (C=C), 138.27 (C=C),
134.56 (C=C), 132.38 (C=C), 131.07 (C=C), 130.63(C=C),
129.47 (C=C), 129.06 (C=C), 124.73 (C=C), 124.09
(C=C), 122.77 (C=C), 114.81 (C=C), 69.26 (F3–C–Ar),
64.24 (O–CH2–Ar), 62.16 (O–CH2), 34.19 (CH2–Ar),
31.13 (CH2–CH2). MS (ESI), (m/z): Calculated: 310.32 ;
Found: 310.19 [M]+. Elemental Analysis, Anal, calc. for
C17H17O2F3: C, 65.78; H, 5.48; Found: C, 65.90; H, 5.00%.
In this study, we reported the synthetic procedures of
3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol
3, phthalonitrile compound 5 and peripherally tetra substi-
tuted metal-free 6, cobalt(II) 7, copper(II) 8, nickel(II) 9 and
iron(II) 10 Pcs. The structures of the synthesized new com-
pounds were identified by several spectroscopic methods.
The electrochemistry and in situ spectroelectrochemistry of
metal-free and metallophthalocyanine containing 4-[3-(4-
{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] groups
on the peripheral positions have been investigated by CV,
SWV and in situ spectroelectrochemistry for understanding
of their redox behaviors.
Synthesis of 4-[3-(4-{[3(trifluoromethyl)benzyl]oxy}phenyl)
propoxy] phthalonitrile (5)
Compound 3 (1.0 g, 3.22 mmol) and 4-nitrophthalonitrile 4
(0.57 g, 3.22 mol) were dissolved in dry DMF (20 ml) and
the solution was stirred at 55–60 °C. Then, powdered dry
K2CO3 (0.16 g, 1.16 mmol) was added to the system in eight
equal portions at 15 min intervals over 2 h. The system was
stirred under N2 at same temperature for 5 days. After this
time, the reaction mixture was poured into ice-water and
stirred at room temperature for 3 h to yield a crude product.
The mixture was filtered and washed with water then dried in
vacuum over P2O5 for 4 h and recrystallized from ethanol but
product didn’t crystallize. Obtained orange oily product was
purified using column chromatography with silicon dioxide
as the column material and a chloroform solvent. Yield: 1.2 g
(85%). IR (KBr tablet), νmax/cm−1: 3074 (Ar–H), 2919–2849
(Aliph. C–H), 2231 (C≡N), 1671–1510 (C=C), 1162–1073
(C–O–C), 968, 827, 798, 700, 660. 1H NMR. (CDCl3), (δ:
ppm): 7.72 (m, 6H, Ar–H), 7.37 (m, 1H, Ar–H), 7.24 (m,
2H, Ar–H), 6.94 (m, 2H, Ar–H), 5.11 (s, 2H, –O–CH2–Ar),
4.15 (t, 2H, –O–CH2), 2.97 (m, 2H, –CH2–Ar), 2.16 (m, 2H,
–CH2–CH2) (Fig. 2). 13C NMR. (CDCl3), (δ: ppm): 162.09,
156.97, 138.12, 135.20, 133.28, 130.59, 129.49, 129.45,
129.07, 124.77, 124.08, 128.47, 119.51, 119.35, 117.44,
115.72 (C≡N), 115.29 (C≡N), 114.97, 114.79, 107.16,
69.28 (F3–C–Ar), 68.08 (O–CH2–Ar), 62.24 (O–CH2), 34.38
Experimental
Materials
The used materials, electrochemical procedure and equip-
ments were supplied as supplementary information.
Synthesis
Synthesis of 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)
propan-1-ol (3)
4-(3-Hydroxypropyl)phenol 1 (1 g, 6.57 mmol) was dis-
solved 50 ml of acetone under N2 atmosphere. Anhydrous
K2CO3 (1.03 g, 7.49 mmol) was added to reaction mixture
then stirring at 60 °C for 15 min. 2 ml 1-(bromomethyl)-
3-(trifluoromethyl)benzene 2 (1.79 g, 7.49 mmol) and
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 1 a 1H NMR spectrum of compound 3, b 1H NMR spectrum of compound 3 with D2O
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 2 1H NMR spectrum of
phthalonitrile compound 5
(CH2–Ar), 30.90 (CH2–CH2). MS (ESI), (m/z): Calculated:
436.43; Found: 437.00 [M+H]+. Elemental Analysis, Anal,
calc. for C25H19N2O2F3: C, 68.81; H, 4.36; N, 6.42; Found:
C, 65.90; H, 5.00; N, 6.85%.
TOF–MS m/z: Calculated: 1747.72 ; Found: 1747.50 [M]+.
Elemental Analysis, Anal, calc. for C100H78N8O8F12: C,
68.68; H, 4.46; N, 6.41; Found: C, 68.02; H, 4.75; N, 6.52%.
Cobalt(II) phthalocyanine (7) Yield: 20 mg (10%). mp:
>300 °C. IR (KBr tablet) νmax/cm−1: 3068 (Ar–CH), 2920–
2850 (Aliph. CH), 1609–1510 (C=C), 1462–1410 (HC=N),
1329, 1231–1161 (C–N), 1117–1071 (C–O–C), 912 (C–H),
795, 660. UV–Vis (CHCI3): λmax, nm (log ε): 666 (5.91),
607 (5.45), 329 (5.86). MALDI–TOF–MS m/z: Calcu-
lated:1804.65; Found: 1805.14 [M+H]+. Elemental Analy-
sis, Anal, calc. for C100H76N8O8F12Co: C, 66.49; H, 4.21; N,
6.20; Found: C, 66.74; H, 4.02; N, 6.57%.
General procedure for synthesis of metalfree (6),
metallophthalocyanines (7–10)
Substituted phthalonitrile 5 and for metallophthalocyanines
corresponding anhydrous metal salts (CoCl2 (14.25 mg,
0.11 mmol); CuCl2 (14.79 mg, 0.11 mmol); NiCl2
(14.26 mg, 0.11 mmol); Fe(Ac)2 (19.12 mg, 0.11 mmol))
were dissolved in 2 ml of DMAE. Then the temperature was
raised to 160 °C and stirred for 4 h under nitrogen atmos-
phere. Methanol was added to the medium and the green raw
products were filtrated and washed with hot ethanol, metha-
nol, n-hexane and diethyl ether. The pure green product was
purified on silica gel column. with chloroform–methanol
(5:1) for compound 6, (5:2) for compound 7, (5:1) for com-
pound 8, (5:2) for compound 9 and 10 solvent system as
eluent. Spectral data of these products are given below.
Copper(II) phthalocyanine (8) Yield: 15 mg (7.5%). mp:
>300 °C. IR (KBr tablet) νmax/cm−1: 3047 (Ar–CH), 2928–
2860 (Aliph. CH), 1595–1509 (C=C), 1484–1460 (HC=N),
1328, 1230–1161 (C–N), 1116–1094 (C–O–C), 879 (C–H),
795, 699. UV–Vis (CHCI3): λmax, nm (log ε): 677 (5.93),
617 (5.50), 329 (5.86). MALDI–TOF–MS m/z: Calculated:
1809.26; Found: 1810.74 [M+H]+. Elemental Analysis,
Anal, calc. for C100H76N8O8F12Cu: C, 66.33; H, 4.20; N,
6.19; Found: C, 66.50; H, 4.33; N, 6.36%.
Metal-free phthalocyanine (6) Yield:
5 mg, (2.5%),
mp>300 °C. IR (KBr tablet) νmax/cm−1: 3292 (–NH), 3034
(Ar–CH), 2919–2850 (Aliph. CH), 1610–1510 (C=C),
1486–1463 (HC=N), 1328, 1233–1161 (C–N), 1117–1096
Nickel(II) phthalocyanine (9) Yield: 12 mg (6%). mp: >
300 °C. IR (KBr tablet) νmax/cm−1: 3056 (Ar–CH), 2926–
2860 (Aliph. CH), 1610–1510 (C=C), 1484–1463 (HC=N),
1328, 1232–1161 (C–N), 1117–1095 (C–O–C), 919 (C–H),
796, 660. 1H NMR. (CDCl3), (δ: ppm): 7.72–7.00 (m, 22H,
Ar–H), 6.99–6.93 (m, 22H, Ar–H), 5.07–5.06 (m, 8H, –O–
CH2–Ar), 4.12 (m, 8H, –O–CH2), 1.57 (m, 16H, CH2).
1
(C–O–C), 957 (C–H), 796, 697. H NMR. (CDCl3), (δ:
ppm): 7.73–7.29 (m, 22H, Ar–H), 7.04–6.99 (m, 22H,
Ar–H), 5.11–5.09 (m, 8H, –O–CH2–Ar), 2.40 (m, 8H, –O–
CH2), 2.30 (m, 16H, CH2). UV–Vis (CHCI3): λmax, nm (log
ε): 702 (6.00), 685 (5.81), 608 (5.54), 390 (5.80). MALDI–
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
UV–Vis (CHCI3): λmax, nm (log ε): 675 (6.02), 615 (5.64),
384 (5.75), 332 (5.87). MALDI–TOF–MS m/z: Calculated:
1804.41; Found: 1805.46 [M+H]+. Elemental Analysis,
Anal, calc. for C100H76N8O8F12Ni: C, 66.50; H, 4.21; N,
6.21; Found: C, 66.09; H, 4.73; N, 6.45%.
The synthesis of 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}
phenyl)propoxy] phthalonitrile 5 was obtained in 85% yield
through base-catalyzed aromatic displacement of 4-nitroph-
thalonitrile with compound 5 using K2CO3 as the base in
dry DMF. In the IR spectrum of phthalonitrile compound 5
was clearly verified with the disappearance of the OH group
of 3 and the presence of C≡N group by the sharp stretch-
ing bands at 2231 cm−1. Other IR stretching vibrations of
5 were similar to compound 3. In the 1H NMR spectrum of
compound 5 at δ = 4.5 ppm (OH group) was disappeared
and the aromatic protons appear at δ=7.72 (m), 7.37 (m),
7.24 (m), 6.94 (m) ppm (Fig. 2). In the 13C NMR spectrum
of compound 5 indicated the presence of nitrile carbon atom
(C≡N) at δ = 115.72–115.29 ppm. In the mass spectra of
phthalonitrile compound 5, the molecular ion peak was
observed at m/z: 437.00 [M+H]+, confirmed the proposed
chemical structure.
Iron(II) phthalocyanine (10) Yield: 10 mg (5%). mp:
> 300 °C. IR (KBr tablet) νmax/cm−1: 3054 (Ar–CH),
2921–2850 (Aliph. CH), 1608–1510 (C=C), 1485–1450
(HC=N), 1328, 1231–1161 (C–N), 1117–1096 (C–O–C),
1
960 (C–H), 796, 699. H NMR. (CDCl3), (δ: ppm): 7.63–
7.57 (m, 22H, Ar–H), 7.56–7.27 (m, 22H, Ar–H), 5.07 (m,
8H, –O–CH2–Ar), 4.09 (m, 8H, –O–CH2), 1.53 (m, 16H,
CH2). UV–Vis (CHCI3): λmax, nm (log ε): 677 (6.00), 622
(5.81). MALDI–TOF–MS m/z: Calculated: 1801.56; found:
1802.50 [M+H]+. Elemental Analysis, Anal, calc. for
C100H76N8O8F12Fe: C, 66.61; H, 4.22; N, 6.22; Found: C,
66.94; H, 4.61; N, 6.83%.
The reaction of phthalonitrile 5 with DMAE gave to the
metal-free phthalocyanine complex 6 and cyclotetrameri-
zation of compound 5 to the peripherally tetra-substituted
metallophthalocyanines (7–10) were accomplished in the
presence of metal salts (CoCl2, CuCl2, NiCl2 and FeCl2)
at 160 °C in DMAE in 4 h under inert atmosphere. These
reactions spoiled under 160 °C in long time such as 12 h,
24 h. We accomplished these reactions in 4 h. In the IR spec-
tra, the formation of phthalocyanine compounds 6–10 was
clearly confirmed by the disappearance of the C≡N band.
IR spectrum of Pcs 6–10 was very similar to each other.
The metal-free phthalocyanine 6 was showed an additional
absorption band at 3292 cm−1 assigned to the NH stretching
vibrations. In the 1H NMR spectrum of metal-free phthalo-
cyanine 6 in CDCl3 the aromatic protons resonated between
7.73 and 6.99 ppm as multiplet and aliphatic protons were
observed at δ=5.11–5.09 (m, 8H, –O–CH2–Ar), 2.40 (m,
8H, –O–CH2), 2.30 (m, 16H, CH2) ppm. The 1H NMR spec-
trum, the NH protons of compound 6 could not be observed
because of the strong aggregation of the molecules [21]. The
MALDI–TOF mass spectrum of compound 6, which showed
a peak at m/z=1747.50 [M]+, confirmed the proposed for-
mula for this compound. showed similar signals because of
the same ring systems. In addition, 1H NMR spectra of the
compound 9 and 10 showed similar signals with compound
6 because of the same ring systems. But, the 1H NMR spec-
tra of complexes 7 and 8 could not be determined owing to
the paramagnetic nature [22]. The MALDI–TOF mass spec-
trum of CoPc 7, CuPc 8, NiPc 9 and FePc 10, the presence
of molecular ion peaks at m/z=1804.65 [M+H]+, 1810.74
[M+H]+, 1804.41 [M+H]+ and 1801.56 [M+H]+ respec-
tively, are in accordance with the expected values.
Results and discussion
Synthesis and characterization
The general synthetic pathway for the synthesis of
3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol
3, phthalonitrile compound 5 and its metalfree 6, cobalt(II)
7, copper(II) 8, nickel(II) 9 and iron(II) 10 phthalocyanine
complexes were given in Fig. 3. All new compounds (3, 5,
6–10) were fully characterised by IR, 1H NMR, 13C NMR
(only 3 and 5), UV–Vis (for compounds 6–10) and MS
spectral data. 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)
propan-1-ol 3 was prepared through base catalyzed reaction
of 4-(3-hydroxypropyl)phenol 1 with 1-(bromomethyl)-3-
(trifluoromethyl)benzene 2 in acetone. The formation of
compound 3 was confirmed by the combination of spectro-
scopic data. In the IR spectra of compound 3, the peak due
to phenolic O–H vibration (3400 cm−1) of 4-(3-hydroxypro-
pyl)phenol disappeared and –CH2–OH and aliphatic C–H
bands (3371 cm−1) appeared, confirming the formation of
compound 3. In the 1H NMR spectra of 3, the phenolic OH
group (δ=4.5 ppm) of compound 3 disappeared, as expected
and showed new signal at δ = 5.10 ppm (Ar–CH2–O) and
δ=3.54 ppm (Aliph OH group) (Fig. 1). The characteristic
13C NMR signals of aromatic carbon atoms at δ: 156.73,
138.27, 134.56, 132.38, 131.07, 130.63, 129.47, 129.06,
124.73, 124.09, 122.77, 114.81; carbon atom belonging
to CF3 group at δ = 69.26 and carbon atoms belonging to
methyl groups at δ = 64.24, 62.16, 34.19 and 31.13 ppm,
supported the structure. The mass spectra of compound 3
confirmed the structure proposed, with the molecular ion
at 310.19 [M]+.
The UV–Vis spectra of the metal-free Pc 6 and MPcs
7–10 show typical electronic spectra with two strong
absorption regions (Q and B bands). In the electronic
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
O
OH
dry K2CO3
18-crown-6
CF3
Br
HO
F3C
HO
acetone
3
2
1
CN
CN
CN
dry K2CO3
dry DMF
CN
O
NO2
CF3
O
4
5
DMAE Metal Salts
CF3
O
F3C
O
O
N
O
N
N
N
M
N
N
N
N
O
6-10
O
O
O
CF3
F3C
Compound
M
6
7
8
9
10
2H Co(II) Cu(II) Ni(II) Fe(II)
Fig. 3 The synthesis route of compounds 3, 5–10
spectra disunited two bands for the metal-free Pc com-
pound 6 and a single Q band for the metallo Pc complexes
(7–10) in CHCl3 at 1 × 10−6 mol dm−3. Characteristic
absorptions in the Q band region were 702/685 nm for
H2Pc 6, 666 nm for compound CoPc 7, 677 for compound
CuPc 8, 675 nm for compound NiPc 9 and 677 nm for
compound FePc 10 in CHCl3. B band absorptions of the
H2Pc 6 and metallophthalocyanines 7–9 were observed at
390, 329, 329, 384–332 nm, respectively (Fig. 4a, b). B
band absorptions of the FePc 10 were not observed and
FePc was aggregation in solvent (Fig. 4).
Voltammetric characterization
The electrochemical behavior of MPcs (Co2+, Cu2+, Fe2+
and Ni2+) to illustrate the effects of metal center of phthalo-
cyanine to the redox properties was investigated via CV and
SWV in DMF involving TBAP as supporting electrolyte.
All of the compounds in the series showed three reductions
and one oxidation (except CoPc and FePc) in determined
the potential window versus Ag/AgCl provided by DMF
(Figs. 5, 6, 7). Different scan rates were performed at CV
measurement (from 25 to 500 mV s−1) for each sample in
series. Half-wave potentials (E1/2), peak to peak separation
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 4 a UV–Vis absorption
spectra changes CoPc, CuPc
and NiPc in CHCl3. b UV–Vis
absorption spectra changes of
FePc and H2Pc in CHCl3
(ΔEp) and ratio of anodic to cathodic peak currents (Ip,a/Ip,c)
were recorded from CV with a scan rate of 100 mV s−1. The
obtained electrochemical data of the complexes are listed
in Table 1.
the CoIIPc−2/[CoIPc−2]− and CoIIPc−2/[CoIIIPc−2]+ redox
couples respectively, and the remaining processes to the
Pc ring. The second and third reduction couples labelled
R2 and R3 are observed at − 1.46 V versus Ag/AgCl and
−2.12 V versus Ag/AgCl, respectively, may be assigned to
[CoIPc−2]−/[CoIPc−3]2− and to [CoIPc−3]2−/[CoIPc−4]3− in
comparison with literature data [23, 24]. For these redox
couples, the cathodic to anodic peak current ratios are
near unity, but the cathodic to anodic peak separations are
130 mV (R1) and 100 mV (R3), suggesting quasi-reversible
behavior, whereas R2 behaves reversible. In addition, the
peak currents for all processes increase linearly with the
square root of scan rates, for scan rates ranging from 25
to 500 mV s−1 which illustrated diffusion controlled mass
transfers during the redox reactions. To shed more light
on the electron-transfer steps of the complexes, UV–Vis
CoPc gives a metal center based one-electron reduc-
tion, R1 and two ring based reductions, R2 and R3 during
the cathodic potential scans. Moreover, during the anodic
scans, a metal based O1 and a Pc based O2 are also observed
(Fig. 5). The first reduction and oxidation reactions of CoPc
occur at small potentials with respect to those of the Pc
based processes (Table 1). It is likely that d-energy levels of
CoPc complex fall between the highest occupied molecu-
lar orbital (HOMO), and the lowest unoccupied molecular
orbital (LUMO) energy levels, and thus it exhibits metal-
based redox processes. The first reduction and the first
oxidation processes of CoPc in DMF could be assigned to
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 6 a CVs of CuPc recorded at various scan rates and b SWVs of
CuPc recorded at 0.100 V s−1 scan rate on a GCE working electrode
in DMF/TBAP electrolyte
Fig. 5 a CVs of CoPc recorded at various scan rates and b SWVs of
CoPc recorded at 0.100 V s−1 scan rate on a GCE working electrode
in DMF/TBAP electrolyte
spectroelectrochemical measurements were carried out. Fig-
ure 8a represents in situ UV–Vis spectral changes during the
first reduction of CoPc at − 0.55 V versus Ag/AgCl, cor-
responding to the redox process labeled R1 in Fig. 5. CoPc
complex displays the Q band at 666 nm with a shoulder
at 606 nm in the Vis-region and the B band at 320 nm in
the UV-region. The Q band shifts to 671 nm, while new
bands at 464 nm and 707 nm appears during the first reduc-
tion process. The band at 464 nm and the shifting of the Q
band indicate formation of [CoIIPc−2]− species, confirming
the CV assignment of the couple R1 process [25–28]. Dur-
ing the second (Fig. 8b) reduction, the Q band at 707 nm
continues to decrease and the absorption between 474 and
946 nm increases. These spectral changes at the potential
of the couples R2 are characteristics for a ring-based reduc-
tion in CoPc complex. Spectral changes observed during
the third reduction process also illustrated the Pc based
character of this process. Figure 8c shows spectral changes
of oxidation processes. The Q band at 666 nm increases in
intensity with red shift to 676 nm. The increase of the Q
band with red shift is characteristic of a metal-based oxida-
tion in CoPc complexes [29]. Therefore, the oxidation pro-
cess, O1 is easily assigned to CoIIPc−2/[CoIIIPc−2]+ process
for couple O1 of CoPc in Fig. 5. Figure 8c (inset of graph)
also shows second oxidation process. During the second
oxidation reaction, the Q band decreases at 676 nm. These
changes indicate Pc-based oxidation process ([CoIIIPc−2]+/
[CoIIIPc−1 2+
] ) for couple O2 of CoPc in Fig. 5. Chroma-
ticity diagram recorded color changes as a result of spec-
tral change during the redox processes is represented in
Fig. 8d. The cyan color (x=0.2665 and y=0.3304) of CoPc
complex turns to light green (x = 0.3446 and y = 0.4064),
then yellow (x=0.4137 and y=0.4275) and at last orange
(x=0.4336 and y=0.4048) during the reduction processes.
During the oxidation reaction, cyan color of CoPc turns to
greenish cyan (x=0.3013 and y=0.3572) and then yellow
color (x=0.3466 and y=0.3608). These multi-color change
properties of CoPc indicates a potential candidate for use as
electrochromic material in window applications [19, 30, 31].
The general voltammetric behaviours of CuPc and NiPc
are like each other [32]. CuPc and NiPc complexes display
three reductions and one oxidation couples as given for CuPc
in Fig. 6. Voltammetric responses of the complex (CuPc and
NiPc) are completely different than those of FePc and CoPc
because just give common Pc based electron transfer reac-
tions [33, 34]. This similarity proposes that all redox pro-
cesses of these complexes are Pc ring-based, having redox
inactive metal center.
The first reduction of the phthalocyanine ligand is equal
to the position of LUMO, while the first oxidation of the
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
ΔE1/2 values of redox-inactive metal center having CuPc
and NiPc are in harmony with the literature [29, 33].
Although CuPc and NiPc illustrated similar voltammetric
responses and had similar redox parameters as shown in
Table 1, there were slight differences between ΔE1/2 val-
ues of the complexes. This difference is possibly stemmed
from the strong withdraw of electrons with increase effec-
tive nuclear charge of metal center of Pc rings. Aggrega-
tion of Pcs in solution to form dimers and higher aggre-
gated forms is based on the concentration, nature of the
solvent, nature of the substituents, metal ion complexes,
and temperature [35, 36]. In comparison with CoPc, CuPc
and NiPc showed more tendency to aggregate in DMF
solution. The aggregation tendency was observed clearly
in situ UV–Vis spectral changes of CuPc. The spectral
changes monitored during the redox processes of CuPc
and NiPc in DMF/TBAP, were similar to each other. When
examined, spectral change of CuPc gives the Q band at
678 nm with a strong aggregation band at 618 nm. This
aggregation is H-aggregation, since it was observed at
the higher energy side of the Q band [37]. Upon the first
reduction of CuPc, the Q band absorption decreases with-
out shift and the appearance of a new absorption bands
were observed at 571 and 950 nm simultaneously during
the redox processes of these complexes (Fig. 9a). These
spectral changes are characteristic for Pc ring-based redox
processes and so, they support the ligand-based nature of
the redox processes of CuPc and NiPc complexes. Dur-
ing the second reduction, new bands appear in the range
of 500–700 nm, while the Q band decreases with broken
of aggregation band (Fig. 9b). Figure 9c shows spectral
Fig. 7 a CVs of FePc recorded at various scan rates and b SWVs of
FePc recorded at 0.100 V s−1 scan rate on a GCE working electrode
in DMF/TBAP electrolyte
ligand is equal to the position of HOMO. In the light of this
information, ΔE1/2 values represent the HOMO–LUMO
gap in MPc species involving redox-inactive metal center.
Table 1 Voltammetric data of
Complexes
Parameters
Redox processes
the complexes
O2
O1
R1
R2
R3
R4
ΔE1/2 (V)
CoPc (in DMF)
E1/2 (V)a
1.42
200
0.25
–
–
–
–
–
–
–
0.38
60
−0.34
130
1.00
−0.76
60
0.99
0.25
60
1.53
−0.76
60
−1.42
60
1.00
−1.15
69
0.94
−0.54
110
1.00
−1.17
60
−2.00
100
0.67
−1.87
110
1.00
−1.09
80
0.87
−1.89
110
–
–
–
–
–
–
ΔEp (mV)b
0.72
c
Ip,a/Ip,c
0.62
0.73
200
0.49
0.90
80
0.93
0.90
130
0.51
CuPc (in DMF)
FePc (in DMF)
NiPc (in DMF)
E1/2 (V)a
ΔEp (mV)b
1.49
0.84
1.66
c
Ip,a/Ip,c
E1/2 (V)a
−1.46
ΔEp (mV)b
70
1.00
–
–
–
c
Ip,a/Ip,c
E1/2 (V)a
ΔEp (mV)b
–
–
c
Ip,a/Ip,c
0.87
0.50
1.00
All data were given versus Ag/AgCl
ΔE1/2 =E1/2 (first oxidation)−E1/2 (first reduction). HOMO–LUMO gap of complexes
aE1/2 values (Epa +Epc)/2 were recorded at 0.100 V s−1 scan rate
b∆Ep =Epa −Epc
cIp,a/Ip,c for reduction, Ip,c/Ip,a for oxidation processes
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 8 In situ UV–Vis spectral
changes of CoPc in DMF/TBAP
electrolyte. a Eapp =−0.55 V, b
E
app =−2.20 V, c Eapp =1.20 V
(inset of graph Eapp =1.60 V),
d Chromaticity diagram
(each symbol represents the
color of electro-generated
species; square: [CoIIPc2−];
circle: [CoIPc2− 1−
] ; right
faced triangle: [CoIPc3− 2−
inverted triangle: [CoIPc4− 3−
star: [CoIIIPc2− 1+
; pentagon:
[CoIIIPc1− 2+
] ;
]
;
]
]
)
changes during the oxidation of the CuPc species, all
bands decrease in intensity due to the decomposition of
the oxidized species of the complex.
give reduction couples at more positive potentials [45, 46].
Although, R1 is observed at positive potentials (at 0.25 V),
FeIIPc illustrates the second metal based process R2 at
−0.54 V. Moreover, at more negative potential, it gives ring
based reduction reactions, R3 at −1.09 V and R4 at −1.46 V.
During the anodic scans, a quasi-reversible oxidation cou-
ple (O1 at 0.90 V) is observed. All redox couples are well
recorded also with SWVs (Fig. 7b).
Color changes recorded during the reduction and oxida-
tion reactions of CuPc, are also represented by the chro-
maticity diagram in Fig. 9d. The color of the solution
changes from light green (x=0.2645 and y=0.3484) to blue
(x=0.2467 and y=0.2865) during the first reduction process
R1. Upon the second reduction, it goes to purple (x=0.2849
and y = 0.2433). On the other hand, the spectral changes
recorded during oxidation process of CuPc are accompanied
by the color changes from green (x=0.2645 and y=0.3484)
to greenish cyan (x=0.3057 and y=0.3380) (Fig. 9d).
Pcs bearing Fe2+ metal centers are rare in the literature
due to the difficulty of the syntheses and instability of these
complexes [38–40], although there are a few papers on the
electrochemistry of Pc bearing Fe3+ metal centers [41–43].
In Fig. 7 shows the CV and SWV for FeIIPc complex in
DMF/TBAP electrolyte system. The complex gives four
reduction and one oxidation processes. The reductions of
metal center of FeIIPc complex indicated a different behavior
from the other [44]. Compared to the literature, FeIIPc can
Spectroelectrochemical measurement for FePc complex
are given in Fig. 10. Upon the first reduction, the Q band
shifts to shorter wavelengths with increasing in the current
intensity (Fig. 10a). Generally, the shifting of the Q band
on the reduction or oxidation suggests a metal-based pro-
cess [47]. Thus the spectral changes shown in Fig. 10a are
typical of a metal-based reduction, assigned to reduction
state of the central Fe(II) to Fe(I). Figure 9b represents the
spectral changes under the applied potential of −1.20 V and
then −1.80 V. While, the intensity of Q band from 665 to
668 nm decreases by shifting, new peaks appear in charge
transfer region at 522 nm and 812 nm. The shift of Q band
and the peak at 526 nm characterize a metal-based reduction
of [FeIIPc−2]0 to [FeIPc−2]1− species. Further reductions are
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 9 In situ UV–Vis spectral
changes of CuPc in DMF/TBAP
electrolyte. a Eapp =−0.90 V, b
E
app =−2.10 V, c Eapp =1.20 V,
d Chromaticity diagram
(each symbol represents the
color of electro-generated
species; square: [CuIIPc2−];
circle: [CuIIPc3− 1−
]
; triangle:
[CuIIPc4− 2−
]
; star: [CuIIPc1− 1+
] )
expected to occur on the ring because of [FeIPc−3]2− spe-
cies. Moreover, intensity of Q band at 668 nm continues
to decrease and new peak observed at 474 nm (inset of
Fig. 10b). Color changes of the complex in solution during
the redox processes were recorded with in situ electrocolori-
metric measurements as shown Fig. 10c. Without any poten-
tial application, the solution of FeIIPc−2 is green (x=0.3395
and y = 0.3724). As the potential is declined from 0.00 to
− 1.80 V, the color of the complex starts to change and a
light yellow (x = 0.3432 and y = 0.3388) and then orange
color (x = 0.4059 and y = 0.3888). Color of the complex
during oxidation reaction turns to yellow (x = 0.3626 and
y=0.3672).
Conclusion
In this paper, we reported the synthetic procedures of
3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol
3, new group substituted phthalonitrile compound 5 and
its metal free 6, cobalt(II) 7, copper(II) 8, nickel(II) 9 and
iron(II)10 phthalocyanine. The obtained new compounds
were characterized by standard spectroscopic methods
(IR, UV–Vis, 1H NMR, 13C NMR, mass spectrometry) and
elemental analysis. Electrochemical characterizations were
performed in order to support the proposed structure of the
complexes and to investigate the effects of the metal cent-
ers and substituents to the general redox behaviors of these
complexes. Multiple reversible and quasi-reversible electron
transfer processes of the complexes at low potentials (espe-
cially for CoPc and FePc) indicate the possible application
of the complexes in different electrochemical technologies
such as electrochromic, electrocatalytic and electrosensor
applications.
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Acknowledgements Authors thank Artvin Coruh University and
Karadeniz Technical University.
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