Polyhedron 48 (2012) 31–42

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Polyhedron
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Peripheral octa-substituted metal-free, cobalt(II) and zinc(II) phthalocyanines

bearing coumarin and chloro groups: Synthesis, characterization, spectral and
electrochemical properties
Selçuk Altun, Ali Rıza Özkaya ⇑, Mustafa Bulut ⇑
Department of Chemistry, Marmara University, 34722 Göztepe, Kadıköy, Istanbul, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: Novel octa-substituted metal-free, cobalt(II) and zinc(II) phthalocyanines have been synthesized by using
Received 15 May 2012 chloro and/or coumarin substituted phthalonitrile derivatives. The compounds were characterized by
Accepted 21 August 2012 UV–Vis, IR, 1H NMR, and MALDI-TOF mass spectrometry and elemental analysis. The effects of substitu-
Available online 12 September 2012
ents, metals, solvents and concentration on spectroscopic properties and aggregation behaviour of the
novel Pcs were investigated. Furthermore, the redox properties of the octa-4-(4-methoxyphenyl)-
Keywords: 7-oxo-8-methylcoumarin-substituted compounds were examined in dimethylsulfoxide and dichloro-
Coumarin
methane by voltammetry and in situ spectroelectrochemistry. Metal-free phthalocyanine and zinc
Phthalocyanine
Octa-substitute
phthalocyanine displayed ligand-based one-electron redox processes whereas cobalt phthalocyanine
Aggregation showed both ligand- and metal-based processes. A couple corresponding to the reduction of
Electrochemistry 4-(4-methoxyphenyl)-7-oxo-8-methylcoumarin substituents was also detected. The redox processes of
the compounds in dimethylsulfoxide were observed to be broad or split, due to the association of electron
transfer processes by aggregation–deaggregation equilibrium.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction Pc compounds have high tendency of aggregation, which is usu-

ally depicted as a coplanar association of rings progressing from
Phthalocyanines (Pcs) form an important class of macrocyclic monomer to dimer and higher order complexes. It is dependent
compounds [1–3] and continue to attract considerable interest as on the concentration, nature of the solvent, peripheral substituents,
pigments [4], dyes [4], sensors [5,6], photodynamic therapy sensi- metal ions and temperature [32,33]. In the aggregated state, the
tizers [7–12], optical recording and nonlinear optical materials electronic structure of the Pc rings is perturbed resulting in alterna-
[13,14], photovoltaics [15], catalysts [16] and electronic device tion of the ground and excited state electronic structure [34].
components [17–19]. Due to the growing interest in the properties In the present work, octa-substituted Pcs bearing only one type
of metal Pcs, the synthesis of new examples involving various func- of substituent (4-(4-methoxyphenyl)-7-oxo-8-methylcoumarin)
tional substituents, with the aim of modifying their properties in 8–10 and both 4-(4-methoxyphenyl)-7-oxo-8-methylcoumarin
the applications listed above, has become necessary. Coumarin and chloro substituents 5–7 were synthesized purely and charac-
(2H-1-benzopyran-2-one) and its derivatives, found naturally in terized by UV–Vis, IR and MALDI-TOF mass spectrometry, and ele-
many higher plants and essential oils including tonka beans, sweet mental analysis (Scheme 1). The effect of these substituents as well
clover and lavender [20,21], are used as anticoagulants [22], addi- as the central metal (Co and Zn), solvent (dimethylsulfoxide
tives in food and cosmetics, in the preparation of insecticides, opti- (DMSO), dichloromethane (DCM), toluene and chloroform) and
cal brighteners and dispersed fluorescent, laser dyes [23–25], anti- concentration on the spectroscopic properties and aggregation
HIV activities, etc. [26]. The family of functional Pcs has been an behaviours of the novel Pcs was also investigated. The understand-
interesting target for chemists for the development of further ing of the redox properties of the Pc complexes is important in
chemical reactions on Pc complexes [27–31]. Therefore, we have terms of their applications in many areas. The redox or electron
combined these two functional materials into a single compound transfer processes of these complexes occur at either the Pc ring
via synthetic methodology to obtain novel Pcs bearing different or the metal center, depending on the central metal and/or the
substituents and metals. solvent medium. However, in most cases, it is not possible to distin-
guish such processes by voltammetry alone. In situ spectroelectro-
⇑ Corresponding authors. Tel.: +90 216 347 96 41; fax: +90 216 347 87 83. chemistry provide additional support for the assignment of these
E-mail addresses: [email protected] (A.R. Özkaya), mbulut@marmar redox processes. Moreover, it is also important in identifying the ef-
a.edu.tr (M. Bulut). fect of aggregation–deaggregation equilibrium of Pcs on their redox

0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.08.080
32 S. Altun et al. / Polyhedron 48 (2012) 31–42

Scheme 1. Synthesis of starting materials (3 and 4) and Pcs (5–10).

behaviour. Therefore, the electrochemical and in situ spectroelect- 2.2. Sample and matrix preparation
rochemical behaviour of the synthesized Pc complexes were also
examined. a-Cyano-4-hydroxycinnamic acid (ACCA) was prepared in tet-
rahydrofuran (THF) at a concentration of 10 mg/mL as matrix.
MALDI samples were prepared by mixing sample solutions
2. Experimental (2 mg/mL in chloroform) and matrix solution (1:10 v/v) in a
0.5 mL EppendorfÒ micro tube. Finally, 0.5 lL of this mixture was
2.1. Material and methods deposited on the sample plate, dried at room temperature, and
then analyzed.
IR Spectra and electronic spectra were recorded on a Shimadzu
FTIR-8300 (KBr pellet) and Shimadzu UV-1601 spectrophotometer,
respectively. Elemental analyses were performed by the Instru- 2.3. Synthesis
mental Analysis Laboratory of Tubitak–Ankara. 1H NMR and 13C
NMR spectra were recorded in d-chloroform with an instrument 2.3.1. 4-Chloro-5-(4-(4-methoxyphenyl)-8-methyl-coumarin-7-
Mercury-Vx 400 MHz. Mass spectra were acquired on Autoflex III yloxy)phthalonitrile 3 and 4,5-bis(4-(4-methoxyphenyl)-8-methyl-
MALDI-TOF mass spectrometer (Bruker Daltonics, Germany) coumarin-7-yloxy) phthalonitrile 4
equipped with a nitrogen UV-laser operating at 337 nm. Spectra 4,5-Dichlorophthalonitrile 1 (1.00 g, 5.08 mmol) and 7-hydroxy-
were recorded in reflectron mode with average of 50 shots. 4-(4-methoxyphenyl)-8-methylcoumarin 2 (5.73 g, 20.32 mmol)
 S. Altun et al. / Polyhedron 48 (2012) 31–42 33

6 3
Fig. 1. The UV–Vis spectra of (A) 5, (B) 6, (C) 7, (D) 8, (E) 9 and (F) 10 in various solvents at 3.0  10 mol dm .

were dissolved in anhydrous dimethylformamide (DMF) (30 mL) 2931, 3042. 1H NMR (CDCl3) d, ppm: 2.20 (s, 6H), 3.74 (s, 6H),
under N2 atmosphere. After stirring for 10 min, finely ground anhy- 6.70 (d, J = 8.99 Hz, 2H), 6.90 (dd, J = 8.99 Hz and J = 2.73 Hz, 4H),
drous K2CO3 (3.50 g, 25.37 mmol) was added by stirring. The reac- 7.03 (s, 2H), 7.11 (s, 2H), 7.25 (dd, J = 8.99 Hz and J = 2.73 Hz, 4H),
tion mixture was stirred at 50 °C for 10 days under N2 atmosphere. 7.33 (d, J = 8.59 Hz, 2H). 13C NMR (CDCl3), d, ppm: 160.95, 160.35,
Then the mixture was poured in 250 ml cold aqueous solution of 5% 155.11, 154.30, 153.97, 150.59, 129.91, 127.19, 125.95, 122.14,
HCl. The formed precipitate was filtered off and washed with water. 118.80, 117.14, 114.85, 114.45, 114.00, 113.99, 111.35, 55.48, 9.00.
After drying in vacuum at 50 °C, the crude product was purified by
column chromatography with silica gel eluting with DCM. Firstly, 2.3.2. General procedure of synthesis of metal-free Pcs 5 and 8
compound 3 and then compound 4 were obtained purely by using The compound 3 (0.20 g, 4.52  10 4 mol) or compound 4
DCM and chloroform as eluting solvents, respectively. (0.20 g, 2.90 x10 4 mol) was heated in 2 ml dry 2-N,N-dimethyl-
Compound 3 is soluble in DCM, chloroform, THF, DMF and aminoethanol in a sealed tube. The mixture was held at 160 °C
DMSO. Mp: 194–196 °C. Yield: 1.30 g (58.04%). Anal. Calc. for C25- for 48 h under N2 atmosphere. After cooling to room temperature,
H15ClN2O4: C, 67.80; H, 3.41; N, 6.33. Found: C, 68.02; H 3.31; N, the reaction mixture was treated with dilute HCl and the mixture
6.42%. IR (KBr pellet) mmax (cm 1): 530, 742, 826, 956, 1079, was filtered and washed with water until the filtrate became neu-
1175, 1245, 1482, 1511, 1578, 1603, 1720, 2235, 2838, 2930, tral. The raw green product was taken in the soxhlet apparatus and
3025, 3096. 1H NMR (CDCl3): d, ppm: 2.20 (s, 3H), 3.75 (s, 3H), then purified by washing with acetic acid, water, ethanol and ace-
6.71 (d, J = 8.59 Hz, 1H), 6.87 (s, 1H), 6.91 (dd, J = 8.59 Hz and tonitrile for 12 h respectively. The crude product was purified on
J = 2.74 Hz, 2H), 7.27 (dd, J = 8.59 Hz and J = 2.73 Hz, 2H), 7.35 (d, column chromatography with silica gel eluting with chloroform a
J = 8.98 Hz, 1H), 7.77 (s, 1H), 7.15 (s, 1H). 13C NMR. (CDCl3), d, gradient of chloroform-THF from 0% to 5% THF.
ppm: 161.04, 160.37, 156.75, 155.02, 154.07, 153.61, 135.77,
129.91, 127.21, 126.18, 120.27, 119.44, 117.62, 115.68, 114.48, 2.3.2.1. 2(3),9(10),16(17),23(24)-Tetrachloro-3(2),10(9),17(16),24(23)-
114.45, 110.47, 55.65, 9.26. tetrakis(4-(4-methoxyphenyl)-8-methylcoumarin-7-yloxy)phthalocya-
Compound 4 is soluble in DCM, chloroform, THF, DMF and nine 5. The compound 5 was obtained and purified as mentioned by
DMSO. Mp: 175–178 °C. Yield: 0.29 g (8.56%). Anal. Calc. for the procedure above for synthesis of metal-free Pcs. This compound
C42H28N2O8: C, 73.25; H, 4.10; N 4.07. Found: C, 73.41; H, 3.98; is soluble in toluene, DCM, chloroform, THF, DMF, dimethylacetamide
N, 4.19%. IR (KBr pellet) mmax (cm 1): 531, 725, 832, 956, 1081, (DMA) and DMSO Mp > 300 °C. Yield: 79.37 mg (58.24%). Anal. Calc.
1173, 1245, 1292, 1365, 1422, 1499, 1603, 1713, 2232, 2838, for C100H62Cl4N8O16: C, 67.73; H, 3.52; N, 6.32. Found: C, 67.55; H,
34 S. Altun et al. / Polyhedron 48 (2012) 31–42

Fig. 2. Positive ion in reflectron mode MALDI-TOF MS spectra of (A) 5, (B) 6, (C) 7, (D) 8, (E) 9 and (F) 10 in a-cyano-4-hydroxycinnamic acid. Inset spectrum shows expanded
molecular ion, sodium and potassium ion adducts mass region of the complex.

3.38; N, 6.46%. IR (KBr pellet) mmax (cm 1): 534, 614, 760, 836, 883, 960, H, 4.17; N, 4.06. Found: C, 73.01; H, 3.99; N, 4.21%. IR (KBr pellet)
1023, 1086, 1177, 1250, 1366, 1440, 1513, 1603, 1645, 1730, 2854, mmax (cm 1): 532, 685,744, 837, 882, 986, 1021, 1085, 1178, 1252,
2924, 2955, 3289. MALDI-TOF mass: m/z 1770.025 (M)+ and 1367, 1433, 1513, 1599, 1645, 1732, 2841, 2865, 2956, 3073, 3298.
1793.664 (M+Na)+. UV–Vis (DCM): kmax (nm), (log e): 310 (5.742), MALDI-TOF mass m/z: 2754.573 (M)+, 2777.742 (M+Na)+. UV–Vis
609 (4.954), 644 (5.289), 678 (5.384), 710 (5.732). 1H NMR. (CDCl3), (DCM): kmax (nm), (log e): 295 (5.316), 343 (5.343), 605 (4.732),
d, ppm: 7.73–6.98 (m, 36H, Ar–H), 3.82 (s, 12H, CH3–O), 2.27 (s, 12H, 632 (4.988), 665 (5.241), 699(5.498).). 1H NMR (CDCl3), d, ppm:
CH3–), 1.48 (s, 2H). 13C NMR (CDCl3), d, ppm: 160.72, 151.80, 135.75, 7.74–6.92 (m, 64H, Ar–H), 3.74 (s, 24H, CH3–O), 2.64 (s, 24H,
135.64, 132.72, 129.99, 127.56, 125.36, 125.05, 114.10, 55.43, 38.01, CH3–), 1.53 (s, 2H).
34.21, 30.46.
2.3.3. General procedure of synthesis of metal Pcs 6,7,9 and 10
2.3.2.2. 2,3,9,10,16,17,23,24-Octakis(4-(4-methoxy-phenyl)-8- A mixture of compound 3 (0.20 g, 4.52  10 4 mol) or com-
methyl-coumarin-7-yloxy)phthalocyanine 8. Compound 8 is soluble pound 4 (0.20 g, 2.90  10 4 mol) with Zn(OAc)2
2H2O (0.13 g,
in toluene, DCM, chloroform, THF, DMF and DMSO. Mp > 300 °C. 5  10 4 mol) or Co(OAc)2.4H2O (0.09 g, 5  10 4 mol) was
Yield: 37.27 mg (35.50%). Anal. Calc. for C168H114N8O32: C, 73.20; powdered in a quartz crucible and transferred in a reaction tube.
 S. Altun et al. / Polyhedron 48 (2012) 31–42 35

Table 1
6 3
Spectral data for Pcs 5–10 in various solvents at 3.0  10 mol dm .

Solvent Pcs Q-band, kmax/nm Log e B-band, kmax/nm Log e

Toluen 5 704, 673, 645, 610 5.603, 5.463, 5.143, 5.010 303 5.654
CHCl3 5 705, 674, 644, 613 5.638, 5.547, 5.125, 4.959 302 5.742
DCM 5 701, 669, 644, 609 5.694, 5.561, 5.141, 4.954 310 5.742
DMSO 5 710, 678, 644, 623 5.732, 5.384, 5.289, 5.267 312 5.784
Toluen 6 679, 615 5.099, 4.756 309 5.292
CHCl3 6 676, 610 5.542, 4.905 317 5.627
DCM 6 678, 610 5.504, 4.830 315 5.573
DMSO 6 659, 629 5.357, 5.337 319 5.694
Toluen 7 679, 652, 612 5.372, 4.602, 4.690 315 5.326
CHCl3 7 680, 651, 613 5.525, 4.746, 4.771 352 5.182
DCM 7 685, 614 5.568, 5.024 336 5.343
DMSO 7 675, 639 5.529, 5.438 345 5.598
Toluen 8 702, 668, 636, 607 5.571, 5.258, 5.917, 4.647 343 5.231
CHCl3 8 700, 665, 635, 605 5.481, 5.276, 4.855, 4.613 345 5.262
DCM 8 699, 665, 632, 605 5.498, 5.241, 4.988, 4.732 343 5.343
DMSO 8 691, 619 5.188, 5.323 334 5.670
Toluen 9 673, 607 5.373, 4.758 311 5.802
CHCl3 9 671, 607 5.414, 4.822 327 5.374
DCM 9 676, 612 5.605, 5.113 312 5.610
DMSO 9 656, 625 5.254, 5.212 320 5.862
Toluen 10 689, 621 5.448, 4.735 295 5.413
CHCl3 10 682, 617 5.673, 4.967 347 5.434
DCM 10 690, 621 5.641, 4.984 313 5.525
DMSO 10 681, 642 5.435, 5.329 342 5.586

0.30 ml of DMF was added to this reaction mixture, and then the
mixture was heated in the sealed glass tube for 20 min under dry
N2 atmosphere at 320 °C. After cooling to room temperature,
3 mL of DMF was added to the residue to solve the product. The
reaction mixture was precipitated by adding acetic acid. The pre-
cipitate was filtered and washed with hot acetic acid, water, etha-
nol and acetonitrile for 12 h in the soxhlet apparatus respectively.
The crude product was purified by column chromatography with
silica gel eluting with chloroform a gradient of chloroform-THF
from 0 to 5% THF.

2.3.3.1. 2(3),9(10),16(17),23(24)-Tetrachloro-3(2),10(9),17(16),24(23)-
tetrakis(4-(4-methoxyphenyl)-8-methylcoumarin-7-yloxy)phthalocyani-
nato cobalt(II) 6. The compound 6 was obtained and purified as ex-
plained by the procedure given above for synthesis of metal Pcs. It is
soluble in toluene, DCM, chloroform, THF, DMF and DMSO.
Mp > 350 °C. Yield: 101.2 mg (74.26%). Anal. Calc. for C100H60Cl4CoN8-
O16: C, 65.62, H, 3.30; N, 6.12. Found: C, 65.85; H, 3.15; N, 5.97%. IR Fig. 3. The UV–Vis spectra of 8 in the range of 3  10 6–1.0  10 7
mol dm 3
in
DMSO. The inset shows the plot of absorbance vs. concentration.
(KBr pellet) mmax (cm 1): 533, 742, 758, 837, 865, 901, 960, 1042,
1086, 1178, 1250, 1278, 1251, 1368, 1415, 1455, 1488, 1513, 1603,
1731, 2865, 2926, 2960. MALDI-TOF mass m/z: 1827.334 (M)+ and
cedure given above. Compound 9 is soluble in toluene, DCM,
1850.125 (M+Na)+. UV–Vis (DCM): kmax (nm), (log e): 315 (2.573),
chloroform, THF, DMF, DMA and DMSO. Mp > 350 °C. Yield:
610 (4.830), 678 (5.504).
40 mg (38.10%). Anal. Calc. for C168H112CoN8O32: C, 71.71; H,
4.01; N, 3.98. Found: C, 71.55; H, 3.86; N, 4.21%. IR (KBr pellet)
2.3.3.2. 2(3),9(10),16(17),23(24)-Tetrachloro-3(2),10(9),17(16),24(23)- mmax/cm 1: 533, 687, 751, 836, 886, 1088, 1109, 1178, 1255,
tetrakis(4-(4-methoxyphenyl)-8-methyl-coumarin-7-yloxy)phthalocyan- 1367, 1403, 1439, 1513, 1598, 1731, 2930, 2957. MALDI-TOF mass
inato zinc(II) 7. The compound 7 was obtained and purified as m/z: 2811.444 (M)+ and 2834.659 (M+Na)+. UV–Vis (DCM): kmax
explained by the procedure explained above. This compound is soluble (nm), (log e): 312 (5.610), 612 (5.113), 676 (5.605).
in toluene, DCM, chloroform, THF, DMF, DMA and DMSO. Mp > 300 °C.
Yield: 95.15 mg (69.82%). Anal. Calc. for C100H60Cl4N8O16Zn: C, 65.39; H,
3.29; N, 6.10. Found: C, 65.61; H, 3.11; N, 5.93%. IR (KBr pellet) mmax 2.3.3.4. 2,3,9,10,16,17,23,24-Octakis(4-(4-methoxyphenyl)-8-methyl-
(cm 1): 527, 566, 604,743, 829, 864, 944, 1024, 1042, 1084, 1114, coumarin-7-yloxy)phthalocyaninato zinc(II) 10. The compound 10
1175, 1247, 1366, 1393, 1422, 1469, 1512, 1595, 1724, 2838, 2933, was obtained and purified as explained by the procedure given
3068. MALDI-TOF mass m/z: 1832.486 (M)+ and 1855.528 (M+Na) +, above. This compound is soluble in toluene, DCM, chloroform,
1871.712 (M+K)+. UV–Vis (DCM): kmax (nm), (log e): 336 (5.343), 614 THF, DMF, DMA and DMSO. Mp > 300 °C. Yield: 58.23 mg
(5.024), 690 (5.568). 1H NMR (CDCl3), d, ppm: 7.80–7.04 (m, 36H, (55.46%). Anal. Calc. for C168H112N8O32Zn: C, 71.55; H, 4.00; N,
Ar–H), 3.85 (s, 12H, CH3–O), 2.61 (s, 12H, CH3–). 3.97. Found: C, 71.44; H, 3.89; N, 4.11%. IR (KBr pellet) mmax
(cm 1): 531, 615,742, 833, 863, 884, 990, 1024, 1079, 1176,
2.3.3.3. 2,3,9,10,16,17,23,24-Octakis(4-(4-methoxyphenyl)-8-methyl- 1245, 1366, 1389, 1422, 1486, 1511, 1596, 1721, 2836, 2936,
coumarin-7-yloxy)phthalocyaninato cobalt(II) 9. A blue-green reac- 2930, 3068. MALDI-TOF mass m/z: 2816.547 (M)+, 2839.669
tion product 9 was obtained and purified as explained by the pro- (M+Na)+ and 2855.621 (M+K)+. UV–Vis (DCM): kmax (nm), (log e):
36 S. Altun et al. / Polyhedron 48 (2012) 31–42

Table 2
Voltammetric data on Pt for 8–10.

Complex Electrolyte Ring oxidations MII/MIII MII/MI Ring reductions Substituent reduction f
DE1/2 Reference
a d
8 (H2Pc) DMSO/TBAP E1/2 (V) 0.51 0.97 tw
e
DEp (V) 0.060 0.100
b d
BS-H2Pc DMSO/TBAP E1/2 (V) 0.56 0.88 31
e
DEp (V) 0.090 0.080
a d
9 (CoPc) DCM/TBAP E1/2 (V) 0.77 1.20 0.19 0.84 1.11 1.58 0.96 tw
e
DEp (V) 0.100 – 0.060 – 0.100 –
c d
DMSO/TBAP E1/2 (V) 0.35 0.41( 0.65) 1.25 1.84 0.76 tw
e
DEp (V) 0.100 0.100 – –
b d
BS-CoPc DMSO/TBAP E1/2 (V) 0.35 0.31 1.24 1.63 0.66 31
e
DEp (V) 0.060 0.060 0.100 0.220
a d
10 (ZnPc) DCM/TBAP E1/2 (V) 1.13 0.65 0.71 1.01 1.63 1.36 tw
e
DEp (V) – 0.080 0.080 0.060 0.200
c d
DMSO/TBAP E1/2 (V) 0.81 (0.91) 0.50 ( 0.63) 0.91( 1.19) 1.62 1.31 tw
e
DEp (V) 0.100 0.060 0.14
b d
BS-ZnPc DMSO/TBAP E1/2 (V) 1.06 0.96 0.55 ( 0.70) 0.81 ( 1.07) 1.65 1.51 31
e
DEp (V) 0.060 0.200 (0.18) 0.200
a
Octa-4-(4-methoxyphenyl)-7-oxo-8-methylcoumarin- substituted phthalocyanine, reported in this study.
b
Previously reported beta-7-oxy-4-(4-methoxyphenyl)-8-methylcoumarin substituted phthalocyanine.
c
The redox behaviour of the compounds in DMSO/TBAP was complicated by aggregation phenomenon and thus, some redox couples were split.
d
E1/2 = (Epa + Epc)/2 at 0.050 V s 1.
e
DEp = Epa Epc (usually at 0.050 V s 1).
f
DE1/2 = E1/2 (first oxidation) E1/2 (first reduction).

313 (5.525), 621 (4.984), 690 (5.641). 1H NMR (CDCl3), d, ppm: starting compounds 3 and 4, respectively (Scheme 1). In fact, the
7.60–6.80 (m, 64H, Ar–H), 3.74 (s, 24H, CH3–O), 2.36 (s, 24H, CH3). phthalocyanine product 5, 6 or 7 was a mixture of its positional iso-
mers due to the involvement of two different substituents (chlorine
and coumarine derivative) in the phthalonitrile precursor. The
2.4. Electrochemistry
photophysical and electrochemical data of the relevant compounds
were obtained from the measurements performed on the mixtures
The cyclic and differential pulse voltammetry measurements
of their isomers.
were carried out with a PAR VersoStat II Model potentiostat/galva-
The characterization of the new products involved a combina-
nostat controlled by an external PC and utilizing a three-electrode
tion of methods including The IR, UV–Vis, 1H NMR and MALDI-
configuration at 25 °C. The working electrode was a Pt plate with a
TOF mass spectrometry and elemental analyses. The results are
surface area of 0.10 cm2. A Pt wire served as the counter electrode.
consistent with the proposed structures.
Saturated calomel electrode (SCE) was employed as the reference
The formation of starting compounds was confirmed clearly by
electrode and separated from the bulk of the solution by a double
the appearance of the new absorption bands at 2232 cm 1 (–C„N)
bridge. Electrochemical grade tetrabutylammonium perchlorate
and 1280 cm 1 (Ar–O–Ar) for 3, and at 2235 cm 1 (–C„N) and
(TBAP) in extra pure DMSO or DCM was employed as the support-
1292 cm 1 (Ar–O–Ar) for 4 in their FT-IR spectra. Compounds 3
ing electrolyte at a concentration of 0.10 mol dm 3. High purity N2
and 4 exhibited –C@C– double bond at 1603 and 1604 cm 1, couma-
was used for deoxygenating the solution at least 20 min prior to
rin carbonyl (lactone, –C@O) at 1720 and 1713 cm 1, –CH3 at
each run and to maintain a nitrogen blanket during the measure-
2838;2930 and 2838;2931 cm 1 and Ar–H stretching frequencies
ments. In situ spectroelectrochemical measurements were carried
at 3070 and 3041 cm 1 respectively. The FT-IR spectra of Pcs 5–10
out by an Agilent Model 8453 diode array spectrophotometer
showed Ar–O–Ar, @C@C–, –C@O, –C@N, –CH3 and aromatic –CH–
equipped with the potentiostat/galvanostat and utilizing an opti-
peaks within the ranges of 1220–1285, 1560–1655, 1760–1780,
cally transparent thin layer cell with three-electrode configuration
at 25 °C. The working electrode was transparent Pt gauze. Pt wire
counter electrode and a SCE reference electrode separated from
the bulk of the solution by a double bridge were used.

3. Results and discussion

3.1. Synthesis and characterization

Octa-substituted Pcs bearing eight 4-(4-methoxyphenyl)-7-oxo-

8-methylcoumarin substituents 8–10 and four chloro substituents
in addition to four 4-(4-methoxyphenyl)-7-oxo-8-methylcoumarin
substituents 5–7 were synthesized and characterized to investigate
differences in their spectroscopic and aggregation behaviours. 4,5-
dichlorophthalonitrile (1) and 7-hydroxy-4-(4-methoxyphenyl)-8-
methylcoumarin (2) have been synthesized by the method in the
literature [35,36]. Unfortunately, despite our all efforts, the reaction
between 1 and 2 produced a mixture of 3 and 4 rather than the
single product of 3 or 4. For this reason, the compounds 3 and 4
in the reaction mixture were separated by column chromatography.
Compounds 5–7 and 8–10 were synthesized by using the new pure Fig. 4. Cyclic voltammograms of 5.0  10 4
mol dm 3
8 in DMSO/TBAP.
 S. Altun et al. / Polyhedron 48 (2012) 31–42 37

1670–1720, 2800–2980 and 3060–3080 cm 1, respectively. The IR-

spectra of the Pcs are very similar, with the exception of metal-free
Pcs 5 and 8, showing a N–H weak stretching band due to the inner
core at 3298, 3289 cm 1 respectively. In addition, disappearing of
–C„N peaks at 2232–2235 cm 1 clearly indicated that starting com-
pounds 3 and 4 were converted to the Pcs 5–10.
The 1H NMR spectra of 3 and 4 showed characteristic signals for
methyl (–CH3) protons at d 2.20 ppm and methoxy (–OCH3) pro-
tons at d 3.75 and 3.74 ppm each a singlet, respectively. The peaks
within the ranges of 6.71–7.15 and 6.70–7.33 ppm indicated the
presence of the aromatic protons in compounds 3 and 4, respec-
tively (Supplementary Materials, Figs. S1 and S2). The 1H NMR
spectra of the Pc compounds 5, 7, 8 and 10 were almost identical
with those of the starting phthalonitrile compounds 3 and 4, ex-
cept broadening and small shifts in the peaks of the formers. The
1
H NMR spectra of 5, 7, 8 and 10 showed aromatic protons signals
within the ranges of 7.73–6.98 ppm for 5, 7.80–7.04 ppm for 7,
7.74–6.92 ppm for 8, and 7.60–6.80 ppm for 10 and aliphatic pro-
tons signals within the range of 3.85–2.27 ppm (–OCH3 and –
CH3) for 5, 7, 8 and 10, as expected (Supplementary Materials, Figs.
S3–S6).
The 13C NMR signals for aromatic and aliphatic (–OCH3 and –
CH3) carbon atoms appeared within the range of 161.04–
110.47 ppm, at 55.65 ppm, and at 9.26 ppm for 3 and within the
range of 160.95–111.35 ppm, at 55.48 ppm and at 9.00 ppm for
4, respectively (Supplementary Materials, Figs. S7 and S8).
The UV–Vis spectra of Pcs 5–10 in various solvents (DMSO,
DCM, toluene and chloroform) showed characteristic Q band
absorptions around 656–705 nm which were attributed to the
p ? p⁄ transitions from the highest occupied molecular orbital
(HOMO) to the lowest unoccupied molecular orbital (LUMO) of
the Pc ring. The other B bands in the UV range 288–352 nm were
due to transitions from the deeper p levels to the LUMO (Fig. 1).
In MALDI-TOF-MS spectra, the molecular ion peaks of 5–10
were observed at 1770.025, 1827.334, 1832.486, 2754.573,
2811.444 and 2816.547 Da, respectively (Fig. 2). Beside the molec-
ular ion peaks of the complexes, sodium ion adducts were also ob-
served. In addition, potassium ion adducts were only observed in
the spectra of zinc Pcs (7 and 10). The complexes showed low frag-
mentation under the MALDI-TOF-MS conditions in reflectron
mode. All high resolved experimental peaks matched perfectly
the theoretical peaks of the complexes determined by isotropic
software calculation. Thus, MS analyses confirmed the molecular
formula of all Pc samples.

3.2. Spectral properties

The Q and B-band absorption data of 5–10 in different solvents

are summarized in Table 1. The split Q-band absorptions of metal-
free Pcs have been observed at 673 and 704 nm, 674 and 705 nm,
and 669 and 701 nm for 5 and at 668 and 702 nm, 665 and 700 nm,
and 665 and 699 nm for 8 in toluene, chloroform and DCM, respec-
tively (Fig. 1A and B). D2h symmetry of 8 causes the splitting of its Fig. 5. Cyclic voltammograms of (A) 5.0  10 4 mol dm 3 (B) 2.0  10 4 mol dm 3
Q-band absorptions. Its split Q-band absorption in non-coordinat- 10 in DMSO/TBAP and (C) 5.0  10 4 mol dm 3 10 in DCM/TBAP. The dotted lines in
ing solvents toluene, chloroform and DCM can be attributed to p– (A) displays differential puls voltammogram of 5.0  10 4 mol dm 3 10 in DMSO/
TBAP.
p⁄ electronic transitions of its monomeric species, but not to the
aggregated species. There are also vibrational absorptions as two
shoulders in its spectrum in the mentioned solvents. The UV–Vis
spectrum of 8 in DMSO involves a broad and weak non-split Q- tions and B-bands appear within the range of 607–621 and 309–
band absorption at 691 nm, in addition to a broad and relatively 352 nm, respectively (Fig. 1C–F and Table 1). However, these com-
much stronger absorption at 619 nm, and the B-band at 334 nm plexes display broad or split absorptions in the Q-band region in
as a single peak (Fig. 1B). DMSO, due to the formation of their aggregated species in this sol-
The UV–Vis spectra of 6, 7, 9 and 10 in non-coordinating sol- vent. The comparison of the molar absorptivity of 6 and 7 with
vents toluene, chloroform and DCM exhibit sharp and non-split those of 9 and 10 shows that the formers involving eight oxy-cou-
Q-band absorptions within the range of 671–690 nm which are marin substituents have lower molar absorptivity than the latters
characteristic for monomeric metal Pcs. Their vibrational absorp- with four oxy-coumarin substituents and four chlorine atoms
38 S. Altun et al. / Polyhedron 48 (2012) 31–42

Fig. 6. In situ UV–Vis spectral changes during controlled-potential electrolysis of 10 in DMSO /TBAP or DCM/TBAP.

(Table 1). This comparison indicates that the aggregation tenden- mately equal at the concentration of 0.10  10 6 mol dm 3. This
cies of the latters are higher than those of the formers, due to observation provides strong evidence for the assignment of the
the increasing intermolecular interactions as a result of the in- band at 619 nm to the H-type aggregates. The aggregation phe-
crease in the number of more electron-withdrawing oxy-coumarin nomenon was also tested by the change of absorbance with con-
substituents. centration within the range of 3.0  10 6 to 1.0  10 7 mol dm 3
Aggregation behaviour of 5–10 was also examined by the spec- in DMSO. The presence of aggregated species was confirmed by
tra monitored at different concentrations in DMSO with the aim of the deviation from Beer–Lambert law (inset in Fig. 3) [37].
providing additional support for the formation of their aggregated The term solvatochromism is used to describe the pronounced
species in this solvent. In general, the decrease in the absorptions change in position (and sometimes intensity) of the UV–Vis
of the blue shifted broad bands was more pronounced than that absorption band, that accompanies a change in the polarity of
of the main Q-band corresponding monomeric species. The spectra the medium. A hypsochromic (or blue) shift with increasing sol-
of 8 at different concentrations in DMSO within the range between vent polarity is usually named negative solvatochromism, while
3  10 6 and 1.0  10 7 mol dm 3 are shown in Fig. 3 as a typical the positive solvathochromism corresponds to a bathochromic
example. As the concentration of 8 is decreased, the decrease in the (or red) shift [38]. Solvent effects on UV–Vis absorption bands of
absorption for the band at 619 nm is more pronounced than that the Pcs was studied in several solvents with different polarities
for the main Q-band and thus, their intensities become approxi- (toluene < DCM < chloroform < DMSO). When UV–Vis spectra of
 S. Altun et al. / Polyhedron 48 (2012) 31–42 39

CoPcs (6 and 9) and ZnPcs (7 and 10) in DMSO (as a polar solvent) in the redox potentials of aggregated and deaggregated species.
compared with in non-polar solvents, 14–17 nm and 7–9 nm the The peripheral nature of the substituents in beta-substituted Pcs,
blue shift were observed respectively. On the other hand, Q absorp- leading to the planarity should be the main reason for the high aggre-
tion bands of metal free Pcs 5 and 8 were shifted 9–12 nm to red gation tendency of these compounds. Fig. 5C shows the cyclic vol-
(Fig. 1 and Table 1). tammograms of 5.00  10 4 mol dm 3 solution of 10 in DCM/TBAP
When the spectrum Pcs 5–7 bearing two different substituents at different scan rates. It also displays three reduction (R1-R3) pro-
(Cl and oxy-coumarin) compared with Pcs 8–10 bearing only one cesses, but two oxidation couples (O1 and O2) due to relatively wide
type of substituent (oxy-coumarin), it was observed that the Q positive potential range available, compared to that in DMSO/TBAP.
band of the 8 and 9 were blue-shifted approximately 5 nm accord- The redox couples of 10 in DCM/TBAP are neither broad nor split
ing to 5 and 6 but 10 were red-shifted approximately 2 nm accord- which shows the absence of aggregated species. The R4 couple,
ing to 7. These UV–Vis spectra show that peripheral substituents of appearing at high negative potentials at the end of solvent-limited
Pcs 5–10 affect their spectral properties weakly (Fig. 1 and Table 1). cathodic potential range in DMSO/TBAP and DCM/TBAP, should cor-
respond to the reduction of 4-(4-methoxyphenyl)-7-oxo-8-methyl-
3.3. Electrochemistry coumarin substituents since these groups, less conjugated as
compared with the Pc ring are expected to be reduced at relatively
The electrochemical behaviour of octa-4-(4-methoxyphenyl)-7- high negative potentials. Anyway, the redox-active nature of oxy-
oxo-8-methylcoumarin- substituted Pcs 8–10 was investigated by coumarin substituents in Pc compounds has been reported previ-
cyclic voltammetry, differential pulse voltammetry and in situ ously [37,40]. It is clear from the well-known redox-inactive nature
spectroelectrochemistry in DMSO and DCM involving tetrabutyl- of metal center in zinc Pcs, other redox processes in DMSO/TBAP and
ammonium perchlorate (TBAP) as supporting electrolyte. The vol- DCM/TBAP (R1, R2, O1 and O2) can be attributed to successive addi-
tammetric data of the complexes, including the half-wave redox tion of electrons to, and removal of an electron from the Pc ring [39].
potential value (E1/2), anodic-to-cathodic peak potential separation However, in situ spectroelectrochemical measurements were car-
(DEp) and the difference between the first oxidation and reduction ried out during the controlled potential electrolysis of 10 in DMSO
potential (DE1/2) are summarized in Table 2 which also includes at a suitable potential corresponding to its first reduction process
the data for recently reported tetra-substituted analogues of 8– since this type of measurements do not only have a vital importance
10 for comparison. in determining the nature of the redox processes, but also provide
Compound 8 displayed two reduction couples (R1 and R2) within
the available potential range in DMSO/TBAP (Fig. 4). These processes
are clearly Pc ring-based since compound 8 is metal-free. As
observed previously for tetra-substituted analogue of 8 [37], the
first oxidation process of 4 is out of the accessible potential range
of DMSO/TBAP medium, probably as a result of the stabilization of
the HOMO and the LUMO, and thus, shifting the redox potentials
towards more positive potentials by 4-(4-methoxyphenyl)-7-oxo-
8-methylcoumarin substituents. Similarly, both cathodic and ano-
dic waves of the first and the second reduction couples (R1 and
R2) of 8 are broad which can be attributed to the presence of its
aggregated species and equilibrium between monomeric and
aggregated species. However, as shown in Table 2, the first reduc-
tion process of 8 occurs at a potential (E1/2 = -0.51 V) somewhat less
negative than that (E1/2 = 0.56 V) of its tetra-substituted analogue
[37]. The separation between the first and second ring reductions is
approximately 0.46 V, which is in agreement with the reported ones
for redox processes in metal-free Pcs [39]. The redox potentials of 8
are less negative than those of the previously reported [39] unsub-
stituted metal-free Pcs in a similar coordinating solvent, DMF, due
to electron withdrawing nature of 4-(4-methoxyphenyl)-7-oxo-8-
methylcoumarin substituents, suggesting that the redox potentials
of Pcs can be changed remarkably by peripheral substituents.
Fig. 5A shows the cyclic and differential pulse voltammograms of
5.00  10 4 mol dm 3 solution of 10 in DMSO/TBAP at different scan
rates. It shows three reduction processes (R1–R3) and an oxidation
couple (O1). As shown in Fig. 5A, the first and second reduction
couples are remarkably broad. The oxidation process (O1) could be
identified only by DPV, due to its high positive potential within the
available potential range. Furthermore, R1, R2 and O1 processes
are split on the differential pulse voltammogram of 10. When the
concentration of the compound was changed from 5.00  10 4 -
mol dm 3 to 2.00  10 4 mol dm 3, the broadness of the R1 and
R2 decreased considerably (Fig. 5B). All these observations indicates
clearly that the electron transfer processes of 10 in DMSO/TBAP are
associated by the equilibrium between aggregated and deaggregat-
ed species. The p–p⁄ interactions between the p-electron clouds of
Fig. 7. Cyclic voltammograms of 5.0  10 4 mol dm 3 9 in (A) DMSO/TBAP (B)
adjacent Pc macrocycles as a result of their coplanar association is DCM/TBAP. The dotted lines in (A) displays differential puls voltammogram of
called as aggregation. This phenomenon results generally in broad- 5.0  10 4 mol dm 3 9 in DMSO/TBAP. The insets in (A) and (B) shows the cyclic
ening of the redox signals or their splitting, due to the differences voltammograms monitored with different switching potentials.
40 S. Altun et al. / Polyhedron 48 (2012) 31–42

support for the evaluation of the aggregation effect on the redox pro- absorption of all bands, occurred during the electrolysis of its solu-
cesses. Fig. 6A and B show the two groups of in situ spectroelectro- tion in DMSO/TBAP at 0.98 V versus SCE, instead of the characteristic
chemical changes, each of which associated with different spectral changes for this process (Fig. 6D). The UV–Vis spectra, mon-
isosbestic points, during the controlled-potential electrolysis of the itored at the beginning of both its first reduction (Fig. 6E) and the first
solution of 10 in DMSO/TBAP at 0.80 V versus SCE. In Fig. 6A, the oxidation (Fig. 6F) of 10 in DCM/TBAP at suitable potentials are not
Q-band absorption in the spectrum at the start of the electrolysis is broad or split, suggesting clearly that it does not form aggregated
split, although the spectroelectrochemical measurements were car- species in DCM/TBAP, as also implied by the cyclic voltammograms
ried out at relatively low concentrations (1.00  10 4 mol dm 3) as recorded in this medium (Fig. 5C). The spectral changes in Figs. 6E
compared to that in voltammetric measurements (5.00  10 4 - and F, the decrease in the Q-band absorption without shift and the
mol dm 3). Therefore, it can be concluded that there is still aggrega- appearance of a new band within the range of 500–600 nm, are char-
tion–deaggregation equilibrium with the high energy band at acteristic for Pc-ring-based redox processes [41,42].
640 nm being due to the aggregate and the low energy band at The cyclic and differential pulse voltammograms of 9 in DMSO/
680 nm due to the monomer. Upon reduction at -0.80 V versus TBAP are shown in Fig. 7A, which involves three reductions (R1,
SCE, the absorption of the aggregation band at 640 nm, decreases R2 and R3) and an oxidation (O1) within the available potential
while that of the monomer band at 680 nm increases with red shift range. The comparison of the two cyclic voltammograms in
to 688 nm, as a first group of spectral changes (Fig. 6A). These spec- Fig. 7A suggests that the shape of the R1 couple is strongly affected
tral changes, characteristic for Pc-ring reduction, are followed by a by the switching potential at the cathodic side. The R3 couple could
decrease in the monomer band without shift and the formation of be monitored only by differential pulse voltammetry. The redox sig-
a new band at 583 nm (Fig. 6B). The two groups of subsequent spec- nals of 9 in DMSO/TBAP are split or broad which leads to ill-defined
tral changes with different isosbestic points indicate clearly that voltammograms. This is probably due to the presence of aggregated
aggregation–deaggregation equilibrium shifts towards to monomer species. The aggregated species are expected to reduce or oxidize at
species before the ligand-based first reduction process. The spectral different potentials in comparison with the deaggregated species,
changes monitored during the second reduction process (R2) at causing the splitting or broadening of the redox signals. The differ-
1.30 V versus SCE, the decrease in the Q-band absorption and the ence between the half-peak potentials of the first oxidation and
formation of a new band at 548 nm, correspond to the reduction of reduction potentials, DE1/2, of 9 is 0.76 V which is much lower in
singly-reduced monomer species (Fig. 6C). Although the O1 process comparison with that of 10. Thus, it is reduced and oxidized more
of 10 could be monitored with differential pulse voltammetry, easily than 10. This distinctive behaviour of 9 can be attributed to
decomposition of the complex, evidenced by the decrease in the the fact that Co(II) center has accessible d orbital levels lying

Fig. 8. In situ UV–Vis spectral changes during controlled-potential electrolysis of 9 in DMSO /TBAP or DCM/TBAP.
 S. Altun et al. / Polyhedron 48 (2012) 31–42 41

between the HOMO and the LUMO gap of the Pc species. In that case, one oxidation couple in DMSO/TBAP within the available potential
metal center can be oxidized and reduced before the ring-based re- ranges. Due to the non-coordinating nature of DCM, the first oxida-
dox processes. This type of Pc complexes can vary their electro- tion processes of 9 (O1) is probably ligand-based and corresponds
chemical behaviour according to their environment, depending on to Co(II)Pc(-2)/[Co(II)Pc(-1)]+ couple while the second one (O2) is
whether there are any available coordinating species that would metal-based and may be attributed to [Co(II)Pc(-1)]+/[Co(III)Pc
stabilize the Co(II) center. The main difference lies in whether the (-1)]2+ couple [39]. Fig. 8D displays the UV–Vis spectrum of 9 in
metal or the ring is oxidized first. Donor solvents strongly favour DCM/TBAP and in situ spectral changes during its first oxidation
Co(III)Pc(-2) by coordinating along the axis to form six coordinate at 1.05 V versus SCE. The solution of complex 9 in DCM/TBAP does
species. If such solvents are absent, then oxidation to Co(III) is inhib- not involve aggregated species as understood clearly from the nar-
ited and ring oxidation occurs first. Thus, the first oxidation and the row and nonsplit Q-band at 671 nm in this figure. Upon the first
first reduction processes of 9 in DMSO/TBAP are probably metal- oxidation, the absorptions of the sharp Q band at 671 nm and the
based and correspond to Co(II)Pc(-2)/[Co(III)Pc(-2)]+ and Co(II)Pc vibrational band at 604 nm decreases without shift and two new
(-2)/[Co(I)Pc(-2)] redox couples, respectively. On the other hand, Q bands at 526 and 755 nm develops. These spectral changes are
it is also well known from the literature that the second reduction characteristic for a Pc-based oxidation and thus, lead to the forma-
process is ring-based [39]. The peak currents of the last reduction tion of [Co(II)Pc(-1)]+ species [41,42]. Unfortunately, the electroly-
couple are much higher than those of the other redox couples, as ob- sis of 9 at the potentials more positive than 1.10 V versus SCE in
served also for 10. This behaviour implies that it corresponds to the DCM/TBAP resulted in decomposition of the complex, as evidenced
reduction of four oxy-coumarin substituents. Spectroelectrochemi- from decrease in the absorption of all peaks.
cal measurements were also carried out to assign especially the first
reduction and the first oxidation processes of 9 certainly. Fig. 8A
4. Conclusions
shows in situ UV–Vis spectral changes during the first reduction of
9 at 0.80 V versus SCE, corresponding to the redox process labelled
The novel metal-free Pcs 5, 8 and metal Pcs 6, 7, 9 and 10 have
R1 in Fig. 7A. The split Q-band absorption in the UV–Vis spectrum of
been prepared from 4-chloro-5-(4-(4-methoxyphenyl)-8-methyl-
9 in DMSO/TBAP confirms the presence of aggregated species. The
coumarin-7-yloxy)phthalonitrile (3) and 4,5-bis(4-(4-methoxy-
band with higher energy corresponds to the aggregated species
phenyl)-8-methylcoumarin-7-yloxy)phthalonitrile (4). The
while the one with lower energy is attributed to the deaggregated
compounds were characterized by UV–Vis, IR and MALDI-
species. Upon the first reduction, the absorptions of both bands de-
TOF mass spectrometry, and elemental analysis. The effect of
crease with red shift, while a new band appears at 475 nm. The new
substituent (the coumarin and chloro), metal (Co and Zn), solvent
Q-band is considerably broad, suggesting that some singly reduced
(DMSO, DCM, toluene and chloroform) and concentration on the
species are still aggregated after the first reduction process. The
spectroscopic properties and aggregation behaviour of the novel
spectral changes form various isosbestic points at different wave-
compounds were investigated. The compounds displayed high
lengths within the ranges of 683–713 nm and 563–573 nm, rather
aggregation tendency in DMSO whereas their aggregated species
than the ones at specific wavelengths, due to the formation of differ-
were not observed in DCM, toluene and chloroform. The
ent reduced species produced from reduction of aggregated and
compounds 8–10 showed redox processes located at the ring
monomer species of 9. The band at 475 nm and the shifting of the
and/or metal centre. The aggregation character of the compounds
Q-band indicate the formation of [Co(I)Pc(-2)] species, confirming
in DMSO was reflected by splitting or broadening of the redox
the CV assignment of the couple R1 to Co(II)Pc( 2)/[Co(I)Pc( 2)]
waves while the compounds displayed well-defined voltammo-
process [36–39]. During the second reduction at 1.50 V versus
grams in DCM, due to the absence of aggregated species in this sol-
SCE, the higher energy side of the broad Q-band at 687 nm decreases
vent. Furthermore, the nature of the redox processes and the effect
while its lower energy side increases, and thus two new bands ap-
of aggregation on the electron transfer processes were identified by
pear at 645 and 702 nm. These spectral changes are associated by
in situ spectroelectrochemical measurements during controlled-
increase in the absorption within the range of 436–625 and thus,
potential electrolysis of the complexes at suitable potentials.
the formation of a band at 492 nm (Fig. 8B). The changes are charac-
teristics for a ring-based reduction in Co(II)Pc complex, and thus,
confirm our voltammetric assignment of this process to [Co(I)Pc Acknowledgments
(-2)] /[Co(I)Pc(-3)]2 . Fig. 8C displays in situ UV–Vis spectral
changes during the first oxidation process at 0.55 V versus SCE. We are thankful to The Foundation of Marmara University,
The absorptions of both peaks of the Q-band decrease and a Q-band The Commission of Scientific Research (BAPKO) (Project No:
with the wavelength maximum of 637 nm and a new band at FEN-A-090909-0302 and FEN-C-DRP-080410-0091) and Turkish
456 nm appears. The new Q-band is considerably broad, suggesting Academy of Sciences (TUBA).
that some singly oxidized species are still aggregated after the first
oxidation process. The formation of a new band at 456 nm is typical Appendix A. Supplementary data
of a metal-based oxidation in CoPc complexes and thus, confirms
the CV assignment of Co(II)Pc(-2)/[Co(III)Pc(-2)]+ for couple O1 of Supplementary data associated with this article can be found, in
9 in Fig. 7A [43–46]. The tetra-substituted analogue of 9 did not the online version, at http://dx.doi.org/10.1016/j.poly.2012.08.080.
form aggregated species in DMSO/TBAP, as stated in a recent report
[37]. It appears that the increase in the number of peripheral oxy-
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