Synthesis and characterization of metallo phthalocyanines bearing 7-oxy-3-(4-pyridyl)coumarin substituents and their supramolecular structures with vanadyl bis(acetylacetonate)

Article abstract of DOI:10.1016/j.poly.2012.03.009

The synthesis of novel zinc and cobalt metallo phthalocyanines with four 7-oxy-3-(4-pyridyl)coumarin dye groups on the periphery/non-periphery were prepared by cyclotetramerization of 7-(3,4-dicyanophenoxy)-3-(4-pyridyl)coumarin (1)/7-(2,3-dicyanophenoxy)-3-(4-pyridyl)coumarin (2) and also a phthalocyanine based on supramolecular structures have been prepared by the ready coordination of pyridine donor sites in 2,9(10),16(17),23(24)-tetrakis[7-oxo-3-(4-pyridyl) coumarin]-phthalocyaninatozinc (1a)/1,8(11),15(18),22(25)-tetrakis[7-oxo-3-(4- pyridyl)coumarin]-phthalocyaninatozinc (2a) with vanadyl bis(acetylacetonate). The novel chromogenic compounds were characterized by elemental analysis, ¹H NMR, Mass spectra, FT-IR and UV-Vis spectral data. The IR-spectra of prepared compounds showed two characteristic intense bands at 1728-1719 cm^-1 for lactone carbonyl and at 1592 cm^-1 for the α, β unsaturated doubled bond.

Full text of DOI:10.1016/j.poly.2012.03.009

Polyhedron 38 (2012) 267–274
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and characterization of metallo phthalocyanines bearing
7-oxy-3-(4-pyridyl)coumarin substituents and their supramolecular structures
with vanadyl bis(acetylacetonate)
Aliye Aslı Esenpınar a, Elif Durmaz b, Fatma Karaca c, Mustafa Bulut b,
⇑
a Kırklareli University, Department of Chemistry, 39100 Kırklareli, Turkey
b Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy, Istanbul, Turkey
c Marmara University, Department of Chemical Engineering, 34722 Kadikoy, Istanbul, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
The synthesis of novel zinc and cobalt metallo phthalocyanines with four 7-oxy-3-(4-pyridyl)coumarin dye
groups on the periphery/non-periphery were prepared by cyclotetramerization of 7-(3,4-dicyanophen-
oxy)-3-(4-pyridyl)coumarin (1)/7-(2,3-dicyanophenoxy)-3-(4-pyridyl)coumarin (2) and also a phthalocy-
anine based on supramolecular structures have been prepared by the ready coordination of pyridine donor
sites in 2,9(10),16(17),23(24)-tetrakis[7-oxo-3-(4-pyridyl)coumarin]-phthalocyaninatozinc (1a)/1,8(11),
15(18),22(25)-tetrakis[7-oxo-3-(4-pyridyl)coumarin]-phthalocyaninatozinc (2a) with vanadyl bis(acetyl-
acetonate). The novel chromogenic compounds were characterized by elemental analysis, 1H NMR, Mass
spectra, FT-IR and UV–Vis spectral data. The IR-spectra of prepared compounds showed two characteristic
Received 28 December 2011
Accepted 7 March 2012
Available online 23 March 2012
Keywords:
Coumarin (2H-1-benzopyran-2-one)
Cobalt
Phthalocyanines
Vanadyl bis(acetylacetonate)
Zinc
intense bands at 1728–1719 cmÀ1 for lactone carbonyl and at 1592 cmÀ1 for the
bond.
a, b unsaturated doubled
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
tions in material sciences [12] such as chemical sensors, photocopy-
ing machines [13–15], Langmuire Blodgett films [16], solar cells,
electrochromism, high energy batteries [17], fibrous assemblies
[18], coloring for plastics and metal surfaces and dyestuffs for cloth-
ing [19], non-linear optics [20], liquid crystals [21], semiconductors
[22], photoconductors, electrochromic displays [23] and gas sensors
[12,24]. Apart from their important contributions in materials sci-
ence, this class of functional dyes also has potential applications
in the treatment of a range of cancers, infectious diseases [25],
and eye and neurodegenerative diseases [26], most of which are re-
lated to the photocytotoxic effects of these compounds.
Unsubstituted Pcs are generally difficult to dissolve in most or-
ganic solvents, hence, limiting their further applications. The intro-
duction of substituents not only improves the solubility but also
modifies their molecular structure, and therefore, the electrical
and optical properties [27]. As a consequence, various kinds of
substituents, which appear to be mainly limited to the electron-
donating groups such as alkyl, alkoxyl, and alkylthio, have been
introduced onto the peripheral/nonperipheral positions of phthalo-
cyanine ligand [28–33]. Phthalocyanines coupled with coumarin
moiety exhibit biological activities [34–36].
Coumarins, the 2H-1-benzopyran-2-one derivatives, are one of
the most important compounds of natural products and in syn-
thetic organic chemistry. They have been used largely in pharma-
ceuticals, perfumery, agrochemical industries as starting material
or intermediate. They are also used as fluorescent brighteners, effi-
cient laser dyes and as additives in food and cosmetics [1–3]. Sev-
eral bioactivities of coumarins, such as antibacterial, anticancer,
inhibitory of platelet aggregation, inhibitory of steroid 5a-reduc-
tase and inhibitory of HIV-1 protease, have also been reported
[1,4–6]. Plants are the most important source of coumarins, but
extraction from plant is tedious, time consuming and needs sophis-
ticated instrumentation. Many synthetic methods, like Pechmann
condensation, Perkin, Reformatsky, Wittig reaction, Knoevenagel
condensation and Claisen rearrangement have been investigated
for the synthesis of coumarins [7–10].
Phthalocyanines (Pcs) are synthetic substances related to the
naturally occurring porphyrins. They consist of a macrocycle made
up of four isoindole units linked by aza nitrogen atoms in contrast
to the methine carbon atoms in porphyrins [11]. Pcs, which were
first developed as pigments, have been found widespread applica-
In this study, phthalocyanines bearing pyridylcoumarin substit-
uents were prepared and their Zn(II), Co(II) metal complexes inves-
tigated. The coumarin contain lactone ring, which is involved in the
pharmaceutical activity. 7-Hydroxy coumarins allow binding this
structure with a Pc by phenoxy bound. This covalent binding
⇑
Corresponding author. Tel.: +90 216 3479641x1370; fax: +90 216 3478783.
E-mail addresses: mustafabulut50@gmail.com,mbulut@marmara.edu.tr(M. Bulut).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.03.009

268
A.A. Esenpınar et al. / Polyhedron 38 (2012) 267–274
should not affect significantly biological activity of the coumarin
moiety. The combined structure and Pc may be a potential candi-
date molecule in the application of photodynamic therapy [28]
and also our choice as a ‘‘capping’’ component was vanadyl bis(ace-
tylacetonate) (VO(acac)2) as this complex has a single empty coor-
dination site and at the same time oxovanadium (VO2+) ions are
known to have important biological functions, for example, in
the case of diabetes [37].
3.00; N, 11.35%. Fluorescence data: (EM) 1 Â 10À5 M, kem: 418 nm
and (EX) 1 Â 10À6 M, kex: 331 nm (DMF). MS (MALDI–TOF): m/z
365 [M]+.
2.1.2. 2,9(10),16(17),23(24)-Tetrakis[7-oxo-3-(4-pyridyl)coumarin]-
phthalocyaninatozinc (1a) and 1,8(11),15(18),22(25)-tetrakis[7-oxo-
3-(4-pyridyl)coumarin]-phthalocyaninatozinc (2a)
7-(3,4-Dicyanophenoxy)-3-(4-pyridyl)coumarin
(1)
(0.10,
0.27 mmol) or 7-(2,3-dicyanophenoxy)-3-(4-pyridyl)coumarin (2)
(0.10, 0.27 mmol) and Zn(CH3COO)2 (0.015 g, 0.068 mmol) were
heated at 160 °C with dry N,N-dimethylaminoethanole (2 ml) in a
sealed tube with stirring for 24 h. After cooling to room tempera-
ture, the reaction mixture was treated with ethanol then filtered
off and washed with water to remove unreacted Zn(CH3COO)2.
The crude green products were purified by extraction with first
nonpolar solvents such as dichloromethane, chloroform, ethylace-
tate, tetrahydrofuran and then polar solvents such as acetonitrile,
acetone, ethanol, methanol, water (approximately 50 ml of each
solvents) and finally purified on silicagel chromatography using
DMF as eluent. The compounds (1a, 2a) are soluble in dimethyl-
formamide and dimethylsulfoxide.
2. Experimental
Routine IR spectra were recorded on a Shimadzu Fourier Trans-
form FTIR-8300 Infrared Spectrophotometer using KBr pellets,
electronic spectra on a Shimadzu UV-1601 UV–Visible Spectropho-
tometer. 1H NMR spectra were recorded on a Varian 500 MHz spec-
trometer in DMSO-d6 for compound. Elemental analysis was
performed by the Instrumental Analysis Laboratory of TUBITAK
Ankara Test and Analysis Laboratory. Mass spectra were performed
on a Bruker Daltonic Autoflex III MALDI–TOF spectrometer. Fluo-
rescence excitation and emission spectra were recorded on a HIT-
ACHI F-7000 Fluorescence spectrophotometer using 1 cm
pathlength cuvettes at room temperatures.
4-Nitrophthalonitrile [38], 3-nitrophthalonitrile [39] and 7-hy-
droxy-3-(4-pyridyl)coumarin [40] were synthesized according to
the reported procedures. N,N-dimethylaminoethanole, dimethyl-
sulfoxide (DMSO) and dimethylformamide (DMF) were dried as
described by Perrin and Armarego [41] before use. Acetone, etha-
nol, chloroform (CHCl3), dichloromethane (DCM), n-hexane, meth-
anol and tetrahydrofuran (THF) were freshly distilled. 2,4-
Dihydroxybenzaldehyde, 4-pyridylacetonitril hydrochloride, pyri-
dine and K2CO3 were purchased from Fluka.
Compound 1a: Yield: 0.06 g (60%). m.p.: >300 °C. IR
3082 (aryl CH), 2850–2925 (alkyl CH), 1724 (C@O lactone), 1471
c
max(cmÀ1):
(C@C), 1602 (C@C), 1265 (Ar–O–Ar). UV–Vis (DMF) kmax (loge)
(nm) (1 Â 10À5 M): 677 (4.16), 335 (4.58). Anal. Calc. for C88H44N12
O12Zn: C, 69.24; H, 2.88; N, 11.01. Found: C, 69.16; H, 2.82; N,
10.98%. Fluorescence data: (EM) 1 Â 10À5 M, kem: 689 nm and (EX)
1 Â 10À6 M, kex: 646 nm (DMF). MS (MALDI–TOF): m/z 1525 [M]+.
Compound 2a: Yield: 0.075 g (75%). m.p.: >300 °C. IR c
max(cmÀ1):
3086 (aryl CH), 2838–2918 (alkyl CH), 1717 (C@O, lactone), 1481
(C@C), 1603 (C@C), 1265 (Ar–O–Ar). UV–Vis (DMF) kmax (loge)
(nm) (1 Â 10À5 M): 689 (4.90), 340 (4.85). Anal. Calc. for C88H44
N12O12Zn: C, 69.24; H, 2.88; N, 11.01. Found: C, 69.22; H, 2.85; N,
11.00%. Fluorescence data: (EM) 1 Â 10À5 M, kem: 704 nm and (EX)
1 Â 10À6 M, kex: 663 nm (DMF). MS (MALDI–TOF): m/z 1525 [M]+.
2.1. Synthesis of Compounds (1,2,1a–c, 2a–c)
2.1.1. 7-(3,4-Dicyanophenoxy)-3-(4-pyridyl)coumarin (1) and 7-(2,3-
dicyanophenoxy)-3-(4-pyridyl)coumarin (2)
7-Hydroxy-3-(4-pyridyl)coumarin (1.00 g, 4.18 mmol) and 4-
nitrophthalonitrile (0.723 g, 4.18 mmol) or 3-nitrophthalonitrile
(0.723 g, 4.18 mmol) were added successively with stirring to dry
DMF (50 ml). After stirring for 15 min, finely ground anhydrous
K2CO3 (0.865 g, 6.27 mmol)) was added portionwise over 2 h and
the mixture was stirred vigorously at room temperature for a fur-
ther 48 h. Then the reaction mixture was poured into water
(150 ml) and the precipitate formed was filtered off, washed with
water. The products (1 and 2) were synthesized as pure. The com-
pounds are soluble in DMF and DMSO.
2.1.3. 2,9(10),16(17),23(24)-Tetrakis[7-oxo-3-(4-pyridyl)coumarin]-
phthalocyaninatocobalt (1b) and 1,8(11),15(18),22(25)-tetrakis[7-
oxo-3-(4-pyridyl)coumarin]-phthalocyaninatocobalt (2b)
7-(3,4-Dicyanophenoxy)-3-(4-pyridyl)coumarin
(1)
(0.10,
0.27 mmol) or 7-(2,3-dicyanophenoxy)-3-(4-pyridyl)coumarin (2)
(0.10, 0.27 mmol) and Co(OAc)2 (0.017 g, 0.06 mmol) were heated
at 160 °C with dry N,N-dimethylaminoethanole (2 ml) in a sealed
tube with stirring for 24 h. After cooling to room temperature,
the reaction mixture was treated with ethanol then filtered off
and washed with water to remove unreacted Co(OAc)2. The crude
green products were purified by extraction with first nonpolar sol-
vents such as dichloromethane, chloroform, ethylacetate, tetrahy-
drofuran and then polar solvents such as acetonitrile, acetone,
ethanol, methanol, water (approximately 50 ml of each solvents)
and finally purified on silicagel chromatography using DMF as elu-
ent. The compounds (1b, 2b) are soluble in dimethylformamide
and dimethylsulfoxide.
Compound 1: Yield: 1.01 g (72%). m.p.: 280 °C. IR (KBr) cmax
(cmÀ1): 3042–3072 (aryl CH), 2950 (alkyl CH), 2233 (C„N), 1728
(C@O lactone), 1487 (C@C), 1592 (C@C), 1291 (Ar–O–Ar). 1H
NMR (DMSO) dH: 7.32 (dd, J = 8.5 ve 2 Hz, 1H), 7.43 (br s, 1H),
7.58 (d, J = 8.5 Hz, 1H), 7.82 (d, J = 4 Hz, 2H), 7.95 (d, J = 8.5 Hz,
2H), 7.99 (t, J = 7.5 Hz, 1H), 8.58 (br s, 1H), 8.73 (br d, J = 4 Hz,
2H). UV–Vis (DMF) kmax (log
e
) (nm) (1 Â 10À5M): 330 (4.15). Anal.
Calc. for C22H11N3O3: C, 72.26; H, 3.01; N, 11.49. Found: C, 71.01; H,
2.98; N, 10.51%. Fluorescence data: (EM) 1 Â 10À5 M, kem: 448 nm
and (EX) 1 Â 10À6 M, kex: 336 nm (DMF). MS (MALDI–TOF): m/z
365 [M]+.
Compound 1b: Yield: 0.055 g (55%). m.p.: >300 °C. IR
c
max(cmÀ1): 3078 (aryl CH), 2866–2925 (alkyl CH), 1728 (C@O, lac-
tone), 1469 (C@C), 1600 (C@C), 1263 (Ar–O–Ar); UV–Vis (DMF)
kmax (log
e
) (nm) (1 Â 10À5 M): 686 (4.13), 337 (4.07). Anal. Calc.
Compound 2: Yield: 1.08 g (72%). m.p.: 290 °C. IR (KBr)
for C88H44N12O12Co: C, 69.51; H, 2.89; N, 11.05. Found: C, 69.48;
c
max(cmÀ1): 3019–3075 (aryl CH), 2946 (alkyl CH), 2231 (C„N),
H, 2.87; N, 11.03%. MS (MALDI–TOF): m/z 1519 [M]+.
1719 (C@O lactone), 1458 (C@C), 1595 (C@C), 1257 (Ar–O–Ar).
1H NMR (DMSO) dH: 7.30 (dd, J = 8.5 ve 2 Hz, 1H), 7.41 (br s, 1H),
7.56 (d, J = 8.5 Hz, 1H), 7.79 (d, J = 4 Hz, 2H), 7.94 (d, J = 8.5 Hz,
2H), 7.98 (t, J = 7.5 Hz, 1H), 8.56 (br s, 1H), 8.70 (br d, J = 4 Hz,
Compound 2b: Yield: 0.08 g (80%). m.p.: >300 °C. IR
3078 (aryl CH), 2940 (alkyl CH), 1725 (C@O, lactone), 1471 (C@C),
c
max(cmÀ1):
1609 (C@C), 1267 (Ar–O–Ar). UV–Vis (DMF) kmax (loge) (nm)
(1 Â 10À5 M): 677 (4.52), 333 (4.65). Anal. Calc. for C88H44N12O12-
Co: C, 69.51; H, 2.89; N, 11.05. Found: C, 69.50; H, 2.88; N,
11.04%. MS (MALDI–TOF): m/z 1519 [M]+.
2H). UV–Vis (DMF kmax (log
Calc. for C22H11N3O3: C, 72.26; H, 3.01; N, 11.49. Found: C, 72.09; H,
e
) (nm) (1 Â 10À5 M): 321 (4.32). Anal.

A.A. Esenpınar et al. / Polyhedron 38 (2012) 267–274
269
Scheme 1. Synthesis of the starting compounds and metallo phthalocyanines.
2.1.4. Peripherally (1c) and nonperipherally substituted (2c)
supramolecular phthalocyanines with vanadyl bis(acetylacetonate)
[4(VO(acac)2)]ZnPc
and finally purified on silicagel chromatography using DMF as elu-
ent. The compounds (1c, 2c) are soluble in DMF and DMSO.
Compound 1c: Yield: 0.048 g (28%). m.p.: >300 °C IR
2,9(10),16(17),23(24)-Tetrakis[7-oxo-3-(4-pyridyl)coumarin]-
phthalocyaninatozinc (1a) (0.1 g, 0.065 mmol) or 1,8(11),15(18),
22(25)-tetrakis[7-oxo-3-(4-pyridyl)coumarin]-phthalocyaninato-
zinc (2a) (0.1 g, 0.065 mmol) and vanadyl bis(acetylacetonate)
(0.14 g, 0.52 mmol) were heated in dry DMF (10 ml) with stirring
at reflux temperature for 6 h. After cooling to room temperature,
the reaction mixture was treated with acetone then filtered off
and washed with ethanol to remove unreacted VO(acac)2. The crude
green products were purified by extraction with first nonpolar sol-
vents such as dichloromethane, chloroform, ethylacetate, tetrahy-
drofuran and then polar solvents such as acetonitrile, acetone,
ethanol, methanol, water (approximately 50 ml of each solvents)
c
max(cmÀ1): 3072 (aryl CH), 2850–2920 (alkyl CH), 1720 (C@O lac-
tone), 1471 (C@C), 1601 (C@C), 1265 (Ar–O–Ar), 1527 and 1373
(acac), 996 (V@O). UV–Vis (DMF) kmax (log
e
) (nm) (1 Â 10À5 M):
673 (4.36), 344 (4.43). Anal. Calc. for C128H100O32N12V4Zn: C,
59.41; H, 3.86; N, 6.49. Found: C, 59.39; H, 3.85; N, 6.40%. Fluores-
cence data: (EM) 1 Â 10À5 M, kem: 687 nm and (EX) 1 Â 10À6 M,
kex: 682 nm (DMF). MS (MALDI–TOF): m/z 2585 [M]+.
Compound 2c: Yield: 0.075 g (30%). m.p.: >300 °C IR
c
max(cmÀ1): 3080 (aryl CH), 2835–2915 (alkyl CH), 1720 (C@O, lac-
tone), 1482 (C@C), 1607 (C@C), 1266 (Ar–O–Ar), 1528 and 1375
(acac), 995 (V@O). UV–Vis (DMF) kmax (log
685 (5.03), 339 (4.94). Anal. Calc. for C128H100O32N12V4Zn: C,
e
) (nm) (1 Â 10À5 M):

270
A.A. Esenpınar et al. / Polyhedron 38 (2012) 267–274
Scheme 2. Synthesis of the nonanuclear supramolecule non-peripheral zinc phthalocyanine.
59.41; H, 3.86; N, 6.49. Found: C, 59.40; H, 3.86; N, 6.45%. Fluores-
cence data: (EM) 1 Â 10À5 M, kem: 706 nm and (EX) 1 Â 10À6 M,
kex: 695 nm (DMF). MS (MALDI–TOF): m/z 2585 [M]+.
obtained 72% for 1 and 2. Cyclotetramerization of the phthalonitrile
derivative 1 or 2 to the metallo phthalocyanines 1a,1b or 2a,2b were
accomplished in 2-N,N-dimethylaminoethanol (DMAE) at 160 °C in
sealed tube. The yields were satisfactory and depended upon the
transition metal ion. The tetrasubstituted phthalocyanine products
were soluble in DMF and DMSO. The crude green products were
purified by extraction with first nonpolar solvents such as dichloro-
methane, chloroform, ethylacetate, tetrahydrofuran and then polar
solvents such as acetonitrile, acetone, ethanol, methanol, water
(approximately 50 ml of each solvents) and finally purified on silica-
gel chromatography using DMF as eluent. Taking into account the
ready coordination of VO(acac)2 with pyridine donors, the interac-
tion of this reagent with peripheral and non-peripheral zinc phthal-
ocyanines were performed in DMF at reflux temperature for 6 h. The
3. Result and discussion
Novel 7-(3,4-dicyanophenoxy)-3-(4-pyridyl)coumarin (1)/7-
(2,3-dicyanophenoxy)-3-(4-pyridyl)coumarin (2) were prepared
by a base catalyzed nucleophilic aromatic nitro displacement of 4-
nitrophthalonitrile/3-nitrophthalonitrile with 7-hydroxy-3-(4-pyr-
idyl)coumarin. The reaction was carried out in a single step synthe-
sis by using K2CO3 as the nitro-displacing base at room temperature
in dimethylformamide under N2 atmosphere and the yields were

A.A. Esenpınar et al. / Polyhedron 38 (2012) 267–274
271
Fig. 1. The positive ion and linear mode MALDI–TOF MS spectrum of 7-(3,4-dicyanophenoxy)-3-(4-pyridyl)coumarin (1) (in the presence of 2,5-dihydroxybenzoic acid (DHB)
(20 mg/ml in THF) as a matrix) were obtained using nitrogen laser accumulating 50 laser shots.
Fig. 2. The positive ion and linear mode MALDI–TOF MS spectrum of supramolecular phthalocyanine (2c) (in the presence of 2,5-dihydroxybenzoic acid (DHB) (20 mg/ml in
THF) as a matrix) were obtained using nitrogen laser accumulating 50 laser shots.
supramolecular dark green solid products (1c and 2c) were obtained
in moderate yield (30%). Characterisation of the products involved a
combination of methods including IR-spectra, elemental analysis,
UV–Vis, fluorescence and MALDI–TOF spectroscopy.
The novel coumarin-substituted phthalocyanines; 1a,1b/2a,2b
and supramolecular structure (2c) from the non-peripheral zinc
phthalocyanine (2a) were prepared according to the route shown
in Schemes 1 and 2.

272
A.A. Esenpınar et al. / Polyhedron 38 (2012) 267–274
0.25
0.16
0.14
0.12
0.1
1a
2a
A
A
0.2
0.15
0.1
0.08
0.06
0.04
0.02
0
0.05
0
300
300
400
500
600
700
800
400
500
600
700
800
Wavelength (nm)
Wavelength (nm)
0.18
0.16
0.14
0.12
0.1
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
B
1b
2b
B
0.08
0.06
0.04
0.02
0
300
400
500
600
700
800
Wavelength (nm)
Fig. 3. UV–Vis spectra of 1a (A) and 2a (B) in DMF (2 Â 10À6 M–1 Â 10À5 M).
300
400
500
600
700
800
Spectral data of the newly synthesized compounds are consis-
tent with the proposed structures. Comparison of the IR spectra data
clearly indicated the formation of compound 1 and 2, the appear-
ance of new absorption bands at 2233 cmÀ1(C„N) and 1291
cmÀ1(Ar–O–Ar) for 1, at 2231 cmÀ1(C„N) and 1257 cmÀ1(Ar–O–
Ar) for 2 (the band OH of 7-hydroxy-3-(4-pyridyl)coumarin at
3141 cmÀ1was disappeared in this spectrum). After conversion of
the dinitrile derivatives (1 or 2) into the phthalocyanines (1a,1b or
2a,2b), the sharp peak for the C„N vibration around 2233 cmÀ1
for 1 and 2231 cmÀ1for 2 disappeared. The IR spectra of the metallo
phthalocyanine 1a,1b/2a,2b were very similar. IR data for 1c and 2c
confirm the presence of a triply bonded terminal oxo ligand (V@O)
995 cmÀ1 and 1373–1527 cmÀ1 (acac).
Wavelength (nm)
Fig. 4. (A) UV–Vis spectra of 1a (1 Â 10À5 M) as compared with that of 2a
(1 Â 10À5 M) in DMF. (B) UV–Vis spectra of 1b (1 Â 10À5 M) as compared with that
of 2b (1 Â 10À5 M) in DMF.
The 1H NMR spectra of 1 and 2 were almost identical except for
small shift; 1H NMR spectrum exhibited lactone protons (C@CH) at
7.43/7.41 ppm (1/2). The aromatic protons of both compounds ap-
peared at 8.73–7.32/8.70–7.30 ppm (1/2).
A closed investigation of the mass spectra of the coumarins and
phthalocyanines confirmed the proposed structure. In the mass
spectra of dicyanophenoxy pyridylcoumarins and metallo phthalo-
cyanines were identified at 365 (1/2) in Fig. 1 at 1525/1519 (1a–b)
at 1525/1519 (2a–b), at 2585 (2c) in Fig. 2, respectively. The
phthalocyanines 1a/1b, 2a/2b and 1c/2c are only soluble in DMF
and DMSO.
The coumarins show maximum absorption with single band at
270–310 nm. UV–Vis spectra of 1/2 in DMF showed a single band
at 330/321 nm.
The phthalocyanines 1a–b/2a–b show typical electronic spectra
with two strong absorption regions, one of them in the UV region
at about 300–350 nm (B band) and the other in the visible part of
the spectrum around 600–700 nm (Q band). Increasing the concen-
Fig. 5. UV–Vis spectra of 2a (1 Â 10À5 M) as compared with that of 2c (1 Â 10À5 M)
in DMF.

A.A. Esenpınar et al. / Polyhedron 38 (2012) 267–274
273
Intensity (a.u)
4NV(EM), 4NV(EX)
Intensity (a.u)
3NV(EM), 3NV(EX)
1000
900
800
700
600
500
400
300
200
100
0
1200
1100
1000
900
800
700
600
500
400
300
200
100
0
E
F
nm
-100
500
500
600
700
800
nm
600
700
800
Wavelength (nm)
Wavelength (nm)
Fig. 6. Fluorescence emission and excitation spectra of 1–2 and 1a, 2a, 1c, 2c in DMF. Excitation wavelength = 336 nm for 1 (A), 331 nm for 2 (B), 646 nm for 1a (C); 663 nm
for 2a (D); 682 nm for 1c (E); 695 nm for 2c (F).
tration leads to aggregation, which is easily observed by the values
of the Q bands, which shift to higher energies by a parallel decrease
in the molar absorption coefficient. Tetrasubstitution with oxygen
bridged groups causes shift (3–18 nm) of the intense Q band to
longer wavelengths when compared with the unsubstituted deriv-
atives. A typical spectrum of the zinc metallo phthalocyanines in
DMF showed a singlet in the Q band region at 678/693–686/
677 nm for 1a/2a–1b/2b and B band region at 344/333–337/
333 nm for 1a/2a–1b/2b (Fig. 3a and b). UV–Vis spectra of 1a/1b
was compared with 2a/2b in Fig. 4. The wavelength of 1a/1b–2a/
2b shifted ꢀ8/ꢀ16 nm to lower energies. The vanadyl phthalocya-
nine (2c) shows the expected Q bands a single absorption at
around 685 nm. The UV–Vis spectra of supramolecular zinc phthal-
ocyanines as compared with peripheral and non-peripheral zinc
phthalocyanines are similar in Fig. 5.
Unsubstituted ZnPc dye is characterized by the band with the
maximum at 673 nm as observed in the literature for ZnPc [27].
ZnPc substituted with four pyridylcoumarin moieties show a bath-
ochromic shift of 5 nm for 1a and 20 nm for 2a.
Fluorescence emission and excitation spectra for ligands (1/2)
and Pcs (1a/2a, 1b/2b and 1c/2c) in DMF were shown in Fig. 6.
Supramolecular peripheral (1c) and non-peripheral (2c) zinc
phthalocyanines have higher fluorescence intensity than 1a and
2a (Table 1). The excitation spectra of the compounds are similar
to that of absorption spectra and are mirror images of the fluores-
cence spectra.

274
A.A. Esenpınar et al. / Polyhedron 38 (2012) 267–274
Table 1
The absorption, excitation and emission wavelengths of the compounds.
Compound
B band kmax (nm)
Q band kmax (nm)
log
e
Excitation kEx (nm)
Emission kEm (nm)
Stokes shift Dstokes (nm)
1
2
330
321
335
337
340
333
344
339
–
–
4.15
4.32
336
331
646
–
663
–
448
418
689
–
704
–
118
97
12
–
15
–
1a
1b
2a
2b
1c
2c
677
686
689
677
673
685
4.16/4.58
4.13/4.07
4.90/4.85
4.52/4.65
4.43/4.36
4.94/5.03
682
695
687
706
14
21
[17] N. Akdemir, E. Ag˘ar, S. Sßaßsmaz, I.E. Gümrükcüog˘lu, T. Çelebi, Dyes and
Pigments 69 (2006) 1.
Acknowledgements
[18] M.N. Yarasir, M. Kandaz, B.F. Senkal, A. Koca, B. Salih, Polyhedron 26 (2007)
We are thankful to the Research Foundation of Marmara Uni-
versity, Commission of Scientific Research Project (BAPKO) FEN-
C-YLP-210311-0061.
5235.
[19] Ö. Bekarog˘lu, Applied Organometallic Chemistry 10 (1996) 605.
[20] D. Dini, M. Hanack, in: K.M. Kadish, K.M. Smith, R. Guilard (Eds.),
Phthalocyanines: Properties and Materials. The Porphyrin Handbook, vol. 17,
Academic Press, New York, 2003, p. 131 (Chapter 107).
[21] N.B. McKeown, Phthalocyanine Materials, Synthesis, Structure and Function,
Cambridge University Press, Cambridge, 1998.
References
[22] M. Hanack, M. Lang, Advanced Materials 6 (11) (1994) 819.
[23] D. Schlettwein, D. Wöhrle, N.I. Jaeger, Journal of the Electrochemical Society
136 (1989) 2882.
[24] S. Dogo, J.P. Germain, C. Maleysson, A. Pauly, Thin Solid Films 219 (1992) 251.
[25] (a) A.M. Rouhi, Chemical Engineering News 2 (1998) 22;
(b) H. Ali, J.E. Van Lier, Chemical Reviews 99 (1999) 2379.
[26] (a) M.J. Rivellese, C.R. Baumal, Lasers 30 (1999) 653;
(b) S.A. Priola, A. Raines, W.S. Cauqhey, Science 287 (2000) 1503.
[27] D. Wrobel, A. Boguta, Journal of Photochemistry and Photobiology A:
Chemistry 150 (2002) 67.
[28] A.A. Esenpınar, M. Durmus, M. Bulut, Spectrochimica Acta A 79 (2011) 608.
[29] A. Esenpınar, A.R. Özkaya, M. Bulut, Polyhedron 28 (2009) 33.
[30] A.A. Esenpınar, M. Bulut, Polyhedron 28 (2009) 3129.
[31] M. Çamur, M. Bulut, Dyes and Pigments 77 (2008) 165.
[32] A. Alemdar, A.R. Özkaya, M. Bulut, Synthetic Metals 160 (2010) 1556.
[33] E. Dur, M. Bulut, Polyhedron 29 (2010) 2689.
[34] A.A. Esenpınar, M. Durmusß, M. Bulut, Spectrochimica Acta A 81 (1) (2011) 690.
[35] A.A. Esenpınar, A.R. Özkaya, M. Bulut, Journal of Organometallic Chemistry 696
(24) (2011) 3873.
[1] O. Kennedy, R. Zhorenes, Coumarins: Biology, Applications and Mode of Action,
John Wiley and Sons, Chichester, 1997.
[2] A. Takadate, T. Tahara, H. Fujino, S. Goya, Chemical Pharmaceutical Bulletin 30
(1982) 4120.
[3] M. Jimeınez, J.J. Mateo, R.J. Mateo, Chromatography A 870 (2000) 473.
[4] G. Cravotto, G.M. Nano, G. Palmisano, S. Tagliapietra, Tetrahedron: Asymmetry
12 (2001) 707.
[5] G.J. Fan, W. Mar, M.K. Park, E. Wook Choi, K. Kim, S. Kim, Bioorganic Medicinal
Chemistry Letters 11 (2001) 2361.
[6] C.J. Wang, Y.J. Hsieh, C.Y. Chu, Y.L. Lin, T.H. Tseng, Cancer Letters 183 (2002)
163.
[7] A. Russell, J.R. Frye, Organic Syntheses 21 (1941) 22.
[8] I. Yavari, R. Hekmat-shoar, A. Zonuzi, Tetrahedron Letters 39 (1998) 2391.
[9] F. Bigi, L. Chesini, R. Maggi, G. Sartori, Journal of Organic Chemistry 64 (1999)
1033.
[10] N. Cairns, L.M. Harwood, D.P. Astles, Perkin Transactions 1 (1994) 3101.
[11] F.H. Moser, A.L. Thomas, The Phthalocyanines, vols. I and II, CRC Press, Inc.,
Boca Raton, 1968.
[12] C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyanines: Properties and Applications,
vol. 1, VCH, New York, 1989 (1993, vols. 2 and 3; 1996, vol. 4).
[13] J. Jiang, K. Kasuga, D.P. Arnold, in: H.S. Nalwa (Ed.), Supramolecular
Photosensitive and Electroactive Materials, Academic Press, San Diego, CA,
2001, p. 188.
[36] M. Çamur, M. Durmußs, A.R. Özkaya, M. Bulut, Inorganic Chimica Acta 383
(2012) 287.
[37] R.M. Mannar, Coordination Chemistry Review 237 (2003) 163.
[38] J.G. Young, W. Onyebuagu, Journal of Organic Chemistry 55 (1990) 2155.
[39] R.D. George, A.W. Snow, Journal of Heterocyclic Chemistry 32 (1995) 495.
[40] O.S. Wolfbeis, H. Marhold, Chemische Berichte 118 (1985) 3664.
[41] D.D. Perrin, W.L.F. Armarego, Purification of Laboratory Chemicals, 2nd ed.,
Pergamon Press, Oxford, 1989.
[14] M. Özer, A. Altındal, A.R. Özkaya, M. Bulut, Ö. Bekarog˘lu, Synthetic Metals 155
(2005) 222.
[15] Ü. Salan, A. Altındal, M. Bulut, Ö. Bekarog˘lu, Tetrahedron Letters 46 (2005) 6057.
[16] E. Hamuryudan, S. Merey, Z.A. Bayir, Dyes and Pigments 59 (2003) 263.