New olefinic centred binuclear clamshell type phthalocyanines: Design, synthesis, structural characterisation, the stability and the change in the electron cloud at olefine-based symmetrical diphthalonitrile fragment by the combined application of UV-Vis

Article abstract of DOI:10.1016/j.poly.2011.03.039

The olefinic centred Schiff base (3) was obtained from the condensation of substituted dialdehyde (1) with 2-amino-4-methylphenol (2) in a 1:2 ratio. The diphthalonitrile derivative (5) was prepared by the reaction of 4-nitrophthalonitrile (4) and compoun

Full text of DOI:10.1016/j.poly.2011.03.039

Polyhedron 30 (2011) 1628–1636
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
New olefinic centred binuclear clamshell type phthalocyanines: Design,
synthesis, structural characterisation, the stability and the change in the
electron cloud at olefine-based symmetrical diphthalonitrile fragment by the
combined application of UV–Vis electronic structure and theoretical methods
a,
a
b
c
⇑
_
Ismail Deg˘irmenciog˘lu , Rıza Bayrak , Mustafa Er , Kerim Serbest
a Department of Chemistry, Faculty of Arts and Sciences, Karadeniz Technical University, 61080 Trabzon, Turkey
b Department of Chemistry, Karabük University, 78050 Karabük, Turkey
c Department of Chemistry, Faculty of Arts and Sciences, Rize University, 53050 Rize, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
The olefinic centred Schiff base (3) was obtained from the condensation of substituted dialdehyde (1)
with 2-amino-4-methylphenol (2) in a 1:2 ratio. The diphthalonitrile derivative (5) was prepared by
the reaction of 4-nitrophthalonitrile (4) and compound (3) in dry dimethylformamide/potassium carbon-
ate. The key product (5) was obtained by nucleophilic substitution of an activated nitro group into an aro-
matic ring. The cyclotetramerization of compound (5) with phthalonitrile (6) in 1:6.15 ratio gave the
expected metal-free phthalocyanine of clamshell type (7), and with metal salts of Zn(II), Ni(II), Co(II)
and Cu(II) gave metallophthalocyanines of clamshell types (8–11), respectively in dimethylaminoetha-
nol/1,8-diazabycyclo[5.4.0]undec-7-ene system. The products were purified by several techniques such
as crystallization and preparative thin layer chromatography. The newly prepared compounds were char-
acterised by a combination of elemental analyses, IR, 1H/13C NMR, MS and UV–Vis spectroscopy.
Ó 2011 Elsevier Ltd. All rights reserved.
Received 26 October 2010
Accepted 22 March 2011
Available online 31 March 2011
Keywords:
Phthalocyanine
Metallophthalocyanine
Binuclear
Clamshell
Schiff’s base
Olefinic centred
1. Introduction
substituted phthalocyanines, mainly because of the difficulties in
preparation and purification [16,17]. In addition, in the last
Phthalocyanines (Pcs), because of their unique properties, have
been a popular class of compounds for chemists since their discov-
ery. Pcs have been used in areas such as chemical sensors, semi-
conductors, liquid crystals, molecular metals, catalysis, non-linear
optics and electrochromism [1,2]. Most of the metal ions can bind
to the cavity of the Pc macrocycle. So many metallophthalocya-
nines have been synthesized so far [2–4]. Metallophthalocyanines
(MPcs) are important because of their rich redox behaviour and
chemical stability [5,6].
While the principle molecules have many useful properties, sci-
entists have attempted considerable effort to achieve novel struc-
tures that may show improved or novel characteristics. In this
connection binuclear Pcs that have different bridges have been
attracted attention [7–10]. Recently, many investigators have been
focused on binuclear phthalocyanines linked by only one bridge,
called as clamshell [11–15]. Many Pc dimers and multimers that
have various kinds of bridges have been reported to date. These
dimers and multimers generally show different electrical, electro-
chemical and spectroscopic properties in proportion to the parent
monomers. Solely, there have been few reports on low-symmetry
few decades scientists have been focused on unsymmetrically
substituted phthalocyanines with different substituents at the
macrocycle fragment [18]. Such phthalocyanines have interesting
characteristics and properties that enable their use as new
technical materials in non-linear optics and photosensitisers in
the photodynamic therapy of cancer [19–23].
In this study, the synthesis, characterisation and structural
investigation of metal-free and metallophthalocyanines of clam-
shell type, which contain olefinic bridge and schiff base moieties,
are described. On the other hand, the substituted diphthalonitrile
5, because it is the starting material of all pcs and a considerable
step compound between the substituted diphenol 3 and function-
alised pcs 7–11, is analysed as part of examination of the role of
the most stable conformation in order to have better interpretation
of its UV–Vis experimental results, with all possible electron tran-
sitions, at density functional theory (DFT) and time-dependent
density functional theory (TD-DFT) calculations.
2. Experimental
All reactions were carried out under an atmosphere of dry, oxy-
gen-free nitrogen, using standard Schlenk techniques. All solvents
were dried and purified as described by Perin and Armarego [24].
⇑
Corresponding author. Fax: +90 462 325 3196.
E-mail address: ismail61@ktu.edu.tr (I. Deg˘irmenciog˘lu).
_
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2011.03.039

_
I. Deg˘irmenciog˘lu et al. / Polyhedron 30 (2011) 1628–1636
1629
4,40-[(2E)-but-2-ene-1,4-diylbis(oxy)]bis(3-methoxybenzalde-
hyde) [25] and 4-nitrophthalonitrile [26] was prepared
Ar-H21), 7.26–7.24 (bd, 4H/Ar-H7,11), 7.20–7.08 (bd, 6H/Ar-
17,5,4), 7.0 (bs, 2H/Ar-H14), 6.87–6.83 (d, 2H/Ar-H13, J = 7.72 Hz),
1
4
H
according to the literature, and 2-amino-4-methyl phenol 2 and
phthalonitrile 6 was purchased from Merck. 1H NMR/13C NMR
spectra were recorded on a Varian XL-200 NMR spectrophotometer
in CDCl3, and chemical shifts were reported (d) relative to Me4Si as
internal standard. IR spectra were recorded on a Perkin–Elmer
Spectrum one FT-IR spectrometer in KBr pellets. The MS spectra
were measured with a Micromass Quattro LC/ULTIMA LC–MS/MS
spectrometer equipped with chloroform–methanol as solvent. All
experiments were performed in the positive ion mode. Elemental
analysis were performed on a Costech ECS 4010 instrument; the
obtained values agreed with the calculated ones. UV–Vis spectra
were recorded by means of a Unicam UV2-100 spectrophotometer,
using 1 cm pathlength cuvettes at room temperature. Melting
points were measured on an electrothermal apparatus and are
uncorrected.
6.12 (bs, 2H/@CHolefinic), 4.69 (bs, 4H, OCH2), 3.81 (s, 6H, OCH3),
2.42 (s, 6H, CH3). 13C NMR (CDCl3) (d: ppm): 162.16 (CH@N),
160.65 (C16), 151.27 (C8), 149.66 (C15), 143.64 (C3), 137.49 (C10),
135.38 (C12), 134.96 (C18), 130.29 (@CHolefinic), 129.23 (C13),
128.34 (C21), 126.61 (C6), 124.33 (C17), 121.97 (C11), 121.20 (C5),
120.65 (C14), 117.87 (C20), 115.57 (C„N), 112.79 (C4), 109.29
(C19), 107.80 (C7), 68.57 (CH2), 56.04 (OCH3), 21.08 (CH3). MS
(ESI) (m/z): Calculated: 818.29; Found: 818.79 [M]+.
2.1.3. Binuclear metal-free phthalocyanine of clamshell type (7)
The solution of compound 5 (0.20 g, 0.244 mmol), phthalonitrile
6 (0.19 mg, 1.5 mmol) in dry N,N-dimethylaminoethanol (DMAE)
(3 mL) and 1,8-diazabycyclo[5.4.0]undec-7-ene (DBU) (0.037 mL,
0.244 mmol) was heated and stirred in a glass sealed tube at
160 °C for 24 h. Then it was diluted with pure water (ca. 30 mL)
and stirred for 12 h. The product was filtered and then washed
with water, hot ethanol, diethyl ether and dried in vacuum over
P2O5. The solid product was chromatographed on preparative sili-
cagel plate (0.5 mm) with chloroform/methanol (5.6:1) as eluents
to give dark green product.
2.1. Synthesis
2.1.1. 2,20-{(2E)-but-2-ene-1,4-diylbis[oxy(3-methoxy-4,1-phenylene)
(E) methylylidene nitrilo]} bis(4-methylphenol) (3)
4,40-[(2E)-but-2-ene-1,4-diylbis(oxy)]bis(3-methoxybenzalde-
hyde) (1) (3.92 g, 0.011 mol) and 2-amino-4-methyl phenol 2
(2.71 g, 0.022 mol) were heated under reflux at 160 °C for 3 h with
no solvent. The crude product was dissolved in 10 mL DMF and fil-
tered then water was added to the filtrate and precipitate was fil-
tered, washed with hot ethanol and dried over P2O5. The
precipitated solid was recrystallised from appropriate solvent
(DMF/ethanol). Yield: 5.23 g (84%).
Yield: 0.0133 g (3.4%), m.p. >300 °C (decomposition). Anal. Calc.
for C98H66N18O6: C, 73.95; H, 4.18; N, 15.84. Found: C, 73.75; H,
4.07; N, 14.70%. IR (KBr tablet)
CH), 2924–2854 (aliph. CH), 1617–1600
1267–1250
m
max/cmꢀ1: 3303 (ANH), 3051
m
(Ar-
m
m(C@C), 1510 m(CH@N),
m
(CAOAC)/(CAN), 1118 d(CAN), 1094 d (ANH) 1035–
1014 d(CAOAC)/(ANH), 971 d(CH). 1H NMR (CDCl3) (d: ppm): 8.34
(s, 2H, CH@N), 7.93–6.69 (bm, 42H/Ar-H), 6.05 (s, 2H/@CHolefinic),
4.56 (s, 4H, OCH2), 3.49 (bs, 6H, OCH3), 2.49 (s, 6H, CH3). UV–Vis
Anal. Calc. for C34H34N2O6: C, 67.41; H, 5.66; N, 4.94. Found: C,
(chloroform): kmax/nm: [(10ꢀ5 log dm3 molꢀ1 cmꢀ1)]: 699 (5.37),
e
67.35; H, 5.60; N, 4.89%. IR (KBr tablet)
3026 (Ar-CH), 2914–2881 (aliph. CH), 1625–1597
(CH@N), 1331 d(AOH), 1271–1225 (CAOAC)/(CAN), 1128
m
max/cmꢀ1: 3349
m
(AOH),
662 (5.32), 641(4.85), 602 (4.73), 339 (5.21), 288 (5.17). MS (ESI)
m
m
m(C@C), 1579
(m/z): Calculated: 1591.69; Found: 1591.84 [M]+.
m
m
d(CAN), 1028–1009 d(CAOAC), 981 d(CH). 1H NMR (CDCl3) (d:
ppm): 12.85 (bs, 2H, OH), 8.57 (s, 2H, CH@N), 7.56 (s, 2H/Ar-H7),
7.34–7.30 (dd, 2H/Ar-H11 J = 8.06 and 1.68 Hz), 7.07–6.88 (m, 8H/
Ar-H5,4,13,14), 6.17 (bs, 2H, @CHolefinic), 4.73 (s, 4H, OCH2), 3.98 (s,
6H, OCH3), 2.31 (s, 6H, CH3). 13C NMR (CDCl3) (d: ppm): 163.24
(CH@N), 151.19 (C8), 147.54 (C3), 146.21 (C15), 136.79 (C10),
136.18 (C12), 130.11 (C6), 129.79 (@CHolefinic), 126.23 (C5), 122.73
(C13), 122.40 (C11), 120.52 (C14), 112.71 (C4), 109.84 (C7), 68.52
(CH2), 56.06 (OCH3), 21.04 (CH3). MS (ESI) (m/z): Calculated:
566.24; Found: 566.44 [M]+.
2.1.4. The general procedure for synthesis of metallophthalocyanines
8–11
A mixture of compound 5 (0.15 g, 0.183 mmol), phthalonitrile 6
(0.14 g, 1.124 mmol), related metal salts (Zn(Ac)2 (0.0716 g,
0.390 mmol); Ni(Ac)2 (0.068 g, 0.390 mmol); CoCl2 (0.051 g,
0.390 mmol); CuCl2 (0.053 g, 0.390 mmol)), dry DMAE (3 mL) and
1,8-diazabycyclo[5.4.0]undec-7-ene (DBU) (0.028 mL, 0.183 mmol)
was heated and stirred in a glass sealed tube at 160 °C for 24 h.
Then it was diluted with pure water (ca. 30 mL) and stirred for
12 h. The product was filtered and then washed with water, hot
ethanol, diethyl ether and dried in vacuum over P2O5. The solid
product was chromatographed on preparative silicagel plate
(0.5 mm) with chloroform/methanol (1:17.5) as eluents to give
dark green product. The chemical and physical spectral character-
istics of these products 8–11 are given below.
2.1.2. 14,40-(2,20-(4,40-(E)-but-2-ene-1,4-diylbis(oxy)bis(3-methoxy-
4,1-phenylene))bis (me-than-1-yl-1-ylidene)bis(azan-1-yl-1-
ylidene)bis(4-methyl-2,1-phenylene))bis(oxy) diphthalonitrile (5)
To a solution of 4-nitrophthalonitrile 4 (0.0613 g, 0.354 mmol)
in dry DMF (15 mL) compound 3 (0.10 g, 0.177 mmol) was added
and the temperature was increased up to 55–60 °C. Powdered
K2CO3 (0.0732 g, 0.531 mmol) was added to the system in eight
equal portions at 15 min intervals with efficient stirring and the
reaction system was stirred at the same temperature for 5 days.
The completeness of the reaction was controlled by thin layer
chromatography (TLC) (chloroform). The temperature of the sys-
tem was lowered to room temperature and poured into ice-water
and mixed overnight. The precipitate was filtered and dried in vac-
uum over P2O5 and recrystallised from ethanol to give dark yellow
crystalline powder. Yield: 0.099 g (68.3%), m.p.: 184–185 °C.
Anal. Calc. for C50H38N6O6: C, 73.34; H, 4.68; N, 10.26. Found: C,
2.1.4.1. Binuclear Zn(II) phthalocyanine of clamshell type (8). Yield:
0.020 g (6.5%), m.p.: >300 °C (decomposition). Anal. Calc. for
C
98H62N18O6Zn2: C, 68.50; H, 3.64; N, 14.67. Found: C, 68.33; H,
3.41; N, 14.63%. IR (KBr tablet) (Ar-CH), 2924–
max/cmꢀ1: 3049
(C@C), 1510 (CH@N), 1267–
m
m
2846
1251
m
(aliph. CH), 1615–1597
m
m
m(CAOAC)/(CAN), 1115 d(CAN), 1031–1013 d(CAOAC), 983
d(CH). 1H NMR (CDCl3) (d: ppm): 8.25 (bs, 2H, CH@N), 7.90–6.91
(m, 42H/Ar-H), 6.19 (s, 2H/@CHolefinic), 4.69 (s, 4H, OCH2), 3.86
(bs, 6H, OCH3), 2.38 (s, 6H, CH3). UV–Vis (chloroform): kmax/nm:
[(10ꢀ5 log dm3 molꢀ1 cmꢀ1)]: 673 (5.21), 610 (4.61), 346 (5.11),
e
283 (4.69). MS (ESI) (m/z): Calculated: 1718.44; Found:
73.41; H, 4.74; N, 10.19%. IR (KBr tablet)
2923–2853 (aliph. CH), 2230 (C„N), 1624–1599
(CH@N), 1270–1250
m
max/cmꢀ1: 3050
(C@C), 1510
m
(Ar-CH),
1718.54 [M]+.
m
m
m
m
(CAOAC)/(CAN), 1112 d(CAN), 1037–1010
2.1.4.2. Binuclear Ni(II) phthalocyanine of clamshell type (9). Yield:
0.019 g (6.2%), m.p.: >300 °C (decomposition). Anal. Calc. for
d(CAOAC), 981 d(CH). 1H NMR (CDCl3) (d: ppm): 8.28 (s, 2H,
CH@N), 7.68–7.63 (d, 2H/Ar-H18, J = 8.39 Hz), 7.43–7.40 (bm, 2H/
C98H62N18Ni2O6: C, 69.03; H, 3.67; N, 14.79. Found: C, 69.12; H,

_
1630
I. Deg˘irmenciog˘lu et al. / Polyhedron 30 (2011) 1628–1636
3.74; N, 14.96%. IR (KBr tablet)
m
max/cmꢀ1: 3051
(C@C), 1508
m
(Ar-CH), 2925–
UV–Vis (chloroform): kmax/nm: [(10ꢀ5 log dm3 molꢀ1 cmꢀ1)]: 679
e
2854
1253
m
(aliph. CH), 1621–1594
m
m(CH@N), 1266–
(5.28), 648 (4.78), 328 (5.13), 231 (5.07). MS (ESI) (m/z): Calculated:
m(CAOAC)/(CAN), 1114 d(CAN), 1028–1015 d(CAOAC), 985
1714.75; Found: 1714.66 [M]+.
d(CH). 1H NMR (CDCl3) (d: ppm): 8.23 (bs, 2H, CH@N), 7.89–6.81
(bm, 42H/Ar-H), 6.17 (s, 2H/@CHolefinic), 4.74 (s, 4H, OCH2), 3.96
(bs, 6H, OCH3), 2.34 (s, 6H, CH3). UV–Vis (chloroform): kmax/nm:
3. Results and discussion
[(10ꢀ5 log dm3 molꢀ1 cmꢀ1)]: 672 (5.20), 645 (4.77), 267 (5.18),
e
3.1. Methods and spectroscopic characterisation via complementary
techniques
246 (5.06). MS (ESI) (m/z): Calculated: 1705.05; Found: 1705.43
[M]+.
The preparation of olefinic centred substituted Schiff bases 3
and 5, the target binuclear metal-free phthalocyanine 7 and met-
allophthalocyanines of clamshell type 8, 9, 10 and 11, is shown
in Fig. 1. The structures of novel compounds have been character-
ised by a combination of 1H/13C NMR, IR, UV–Vis, elemental anal-
ysis and MS spectral data.
2.1.4.3. Binuclear Co(II) phthalocyanine of clamshell type (10). Yield:
0.021 g (6.8%), m.p.: >300 °C (decomposition). Anal. Calc. for
C98H62Co2N18O6: C, 69.01; H, 3.66; N, 14.78. Found: C, 69.17; H,
3.61; N, 14.63%. IR (KBr tablet)
2851 (aliph. CH), 1617–1596
(CAOAC)/(CAN), 1119 d(CAN), 1035–1016 d(CAOAC), 981 d(CH).
UV–Vis (chloroform): kmax/nm: [(10ꢀ5 log dm3 molꢀ1 cmꢀ1)]: 679
m
max/cmꢀ1: 3049
(C@C), 1511 (CH@N), 1281–1257
m(Ar-CH), 2917–
m
m
m
m
e
3.1.1. Synthesis of precursor 3
(5.23), 650 (4.78), 310 (5.13), 247 (5.20). MS (ESI) (m/z): Calculated:
Functionalised olefinic centred Schiff base 3 was synthesized at
considerably high temperature with no solvent. The IR spectra
were used to identify substituents appearing or disappearing from
the periphery of the related compounds. In the IR spectrum of 3,
stretching vibration peaks of NH2 group of reactant 2 at 3344–
3321 cmꢀ1 and aldehyde group of 1 at 1690 cmꢀ1 were not pres-
ent, and that indicates the amino and aldehyde groups have been
converted to Schiff base. In addition, a new band at 1579 cmꢀ1
corresponding to imine group of 3 proves the condensation has
1705.53; Found: 1705.12 [M]+.
2.1.4.4. Binuclear Cu(II) phthalocyanine of clamshell type (11). Yield:
0.023 g (7.5%), m.p.: >300 °C (decomposition). Anal. Calc. for
C
98H62Cu2N18O6: C, 68.64; H, 3.64; N, 14.70. Found: C, 68.54; H,
3.81; N, 14.55%. IR (KBr tablet) (Ar-CH), 2926–
max/cmꢀ1: 3045
2862 (aliph. CH), 1617–1597
m
m
m
m(C@C), 1506
m
(CH@N), 1267–1254
m(CAOAC)/(CAN), 1020 d(CAN), 1028–1015 d(CAOAC), 973 d(CH).
O
CN
CN
O
2
N
OH
O
i
O
O
2
H2N
HO
O
O2N
O
HO
N
O
O
O
4
3
1
2
ii
NC
22
23
11
O
12
13
14
NC
2
8
7
10
2
N
B
O
3
6
O
A
15
O
CN
CN
O
1
9
1
21
6
N
3
20 CN
4
5
16
17
O
C
19
CN
18
6
5
iii
N
N
N
N
N
N
N
M
N
O
N
O
O
O
O
N
O
N
N
N
N
N
N
o
M
N
i:solventfree/160 C
o
N
ii: dry DMF, dry K CO , N , 55-60 C
iii: 24 h, DMAE / DBU, 160 C, Metal free, dry Zn(CH COO) ,
2
3
2
o
3
2
Compound
M
7
8
9
10 11
dry Ni(CH COO) , dry CoCl ,
3
2
2
2H Zn Ni Co Cu
dryCuCl
2
Fig. 1. Synthetic route of novel compounds.

_
I. Deg˘irmenciog˘lu et al. / Polyhedron 30 (2011) 1628–1636
1631
occurred. The rest of the spectrum of 3 was similar those of 1 and 2
iminic protons of
3
were also observed at 12.85 ppm and
involving the characteristic vibrations of aliphatic, olefinic and
phenolic groups. 1H NMR spectrum of 3 had many differences from
the spectrum of 1 and 2. The difference between the spectra of 1
and Schiff base 3 has been clearly seen to arise from the absence
of aldehyde group at 10.01 ppm. In addition, peaks of the amino
group of 2 at 8.01 ppm were not observed in the spectrum of 3
too. Furthermore, D2O exchangeable phenolic AOH protons and
8.57 ppm, respectively. Furthermore, the MS mass spectrum of 3
showed a molecular ion peak at m/z = 566.44 [M]+, supporting
the proposed formula for this compound.
3.1.2. Synthesis of substituted diphthalonitrile 5
Diphthalonitrile derivative 5 was obtained from the reaction of
diphenol derivative 3 with 4-nitrophthalonitrile 4 in dry DMF/dry
K2CO3 under N2 atmosphere at 60 °C in schlenk system, for 5 days.
This is achieved by base catalysed nucleophilic aromatic nitro dis-
placement of 4-nitrophthalonitrile with 3 [27–29]. Spectral inves-
tigations for the new product were consistent with the assigned
structure. IR spectra, taken with KBr pellets, clearly indicated the
formation of compound 5, by the disappearance of AOH stretch-
ing/deformation of 3 at 3349/1331 cmꢀ1 and NO2 stretching of
compound 4 at 1519, 1333 cmꢀ1 and by the appearance of C„N
absorption band at 2230 cmꢀ1. Its 1H NMR spectrum, which was
taken in chloroform-d, was also in good correlation with the struc-
ture of the synthesized compound. D2O exchangeable phenolic
AOH at 12.85 ppm disappeared after condensation. Furthermore,
in the aromatic region, four doublets at ca. d = 7.68–7.63 (H18),
7.26–7.24 (H7,11), 7.20–7.08 (H4,5,17), 6.87–6.83 ppm (H13) and a
broad singlet at ca. d = 7.0 (H14) and broad multiplet at ca. 7.43–
7.40 (H21) are observed in the spectrum, respectively. Additionally,
1H NMR spectrum of compound 5 showed five singlets at d = 8.28
(ACH@N), 6.12 (HC@CH), 4.69 (OCH2), 3.81 (OCH3) and 2.42 ppm
(CH3) as expected. The proton-decoupled 13C NMR spectrum indi-
cated the presence of nitrile carbon atoms in compound 5 at
115.57 ppm. In addition, the MS mass spectrum of 5 showed a
molecular ion peak at m/z = 818.79 [M]+, supporting the proposed
formula for this compound.
2
1.5
1
0.5
0
200
300
400
500
600
700
800
900
λ ( nm )
Fig. 2. UV–Vis spectra of compounds 7 (––) and 8 (ꢁ ꢁ ꢁ ꢁ) in CHCl3.
2
3.1.3. Synthesis of metal free 7 and metallophthalocyanines 8–11
The unsymmetrical metal free phthalocyanine 7 was synthe-
sized by statistical cross-condensation of a 1:6.15 molar ratio of 5
and 6 in DMAE/DBU by heating under reflux for 24 h. In case of met-
allophthalocyanines, addition to the substituted diphthalonitrile 5
and phthalonitrile 6, four metal salts, Zn(CH3COO)2, Ni(CH3COO)2,
CoCl2, CuCl2 were used as templates for the formation of 8, 9, 10
and 11 respectively. It is known that statistical cross-condensation
of phthalonitriles gives the mixture of phthalocyanines, however,
this method is commonly used for the preparation of different
unsymmetrical Pcs [28,29]. Statistical considerations predict that
when two phthalonitriles A and B (if they have same reactivity)
1.5
1
0.5
0
200
300
400
500
600
700
800
900
λ ( nm )
Fig. 3. UV–Vis spectra of compounds 9 (––), 10 (–ꢁ–ꢁ) and 11 (ꢁ ꢁ ꢁ ꢁ ꢁ ꢁ) in CHCl3.
Table 1
The spin-allowed singlet–singlet electronic transitions with the TD-DFT method and the assignments of the calculated transitions to the experimental absorption bands of 5 with
aZZZa conformer (a denotes HOMO, b denotes LUMO and Lp denotes nonbonding).
The most important
orbital excitations
Transitions with major/
minor contributions
Oscillator (f)
kexp (nm)
kcalc (nm)
Character
Hꢀ2 ? L+1
Hꢀ1 ? L
aH ? L+1
Hꢀ5 ? L
Hꢀ5 ? L+2
Hꢀ3 ? L
Hꢀ1 ? L+2
H ? bL
212 ? 216 (6%)
213 ? 215 (37%)
214 ? 216 (86%)
209 ? 215 (2%)
209 ? 217 (4%)
211 ? 215 (3%)
213 ? 217 (40%)
214 ? 215 (80%)
214 ? 218 (60%)
210 ? 218 (2%)
212 ? 218 (18%)
214 ? 215 (20%)
214 ? 217 (80%)
211 ? 215 (3%)
211 ? 217 (2%)
213 ? 215 (49%)
213 ? 217 (40%)
0.071
332
330
Lpnitrile/LpO1–3
Lpnitrile/LpO1–3
Lpnitrile/LpO1–3
?
?
?
r⁄
r⁄
r⁄
?
?
A
A
A
p⁄
ring/C„N/CH@N/O3
ring/C„N/CH@N/O3
ring/C„N/CH@N/O3
p⁄C
p⁄C
0.116
312
319
Lpazomethine/LpO1–3
r⁄C
A
A
p⁄
ring/C„N/CH@N/O3
Lpazomethine/LpO1–3
r⁄
p⁄C
A
ring/C„N/CH@N/olefinic carbons/O1
LpO3
?
r⁄
A
p⁄
C
ring/C„N/CH@N/O3
Lpnitrile/LpO1–3
Lpnitrile/LpO1–3
Lpnitrile/LpO1–3
?
?
?
r⁄
r⁄
r⁄
A
A
A
p⁄
p⁄A
ring/C„N/CH@N/olefinic carbons/O1
ring/C„N/CH@N/O3
H ? L+3
1.109
0.098
287
262
297
273
p⁄C
A
ring/C„N/CH@N/CH2/O1
Hꢀ4 ? L+3
Hꢀ2 ? L+3
H ? L
LpO3
?
r⁄
A
p⁄
A
ring/C„N/CH@N/CH2/O1
Lpnitrile/LpO1–3
Lpnitrile/LpO1–3
Lpnitrile/LpO1–3
?
?
?
r⁄
r⁄
r⁄
A
A
A
p⁄
p⁄A
ring/C„N/CH@N/CH2/O1
ring/C„N/CH@N/O3
H ? L+2
p⁄C
A
ring/C„N/CH@N/olefinic carbons/O1
Hꢀ3 ? L
Hꢀ3 ? L+2
Hꢀ1 ? L
Hꢀ1 ? L+2
1.019
239
253
LpO3
LpO3
?
?
r⁄
A
A
p⁄
ring/C„N/CH@N/O3
r⁄
p⁄C
A
ring/C„N/CH@N/olefinic carbons/O1
Lpnitrile/LpO1–3
Lpnitrile/LpO1–3
?
?
r⁄
A
A
p⁄
ring/C„N/CH@N/O3
r⁄
p⁄C
A
ring/C„N/CH@N/olefinic carbons/O1

_
1632
I. Deg˘irmenciog˘lu et al. / Polyhedron 30 (2011) 1628–1636
react together in the ratio 3:1 will give a mixture of the symmetric
Pc (AAAA), and the desired 3:1 Pc (AAAB) and other cross-conden-
sation products [30,31]. Such an approach leads to a mixture of
mainly two products, unsubstituted symmetric Pc and desired
asymmetric Pc. Chromatographic purification was performed to
obtain the desired products. In order to reduce the purification
problems we chose phthalonitrile 6 and used excess, because it is
known that the solubility of the unsubstituted symmetric Pc in
common organic solvents is very low [32]. Therefore, after known
classical solvent washings, these unsymmetrical Pcs were isolated
by preparative silicagel chromatography plate using chloroform/
methanol solvent system. The solubilities of the clamshell type
phthalocyanines were good in common organic solvents such as
chloroform, ethyl acetate, acetone, tetrahydrofurane and ethanol.
The spectroscopic characterisation of the newly synthesized
compounds includes 1H NMR, IR, UV–Vis and mass spectral inves-
tigations, and the results are in accordance with the proposed
structures. Cyclotetramerization of dinitriles 5 and 6 to Pcs 7, 8,
9, 10 and 11 was confirmed by the disappearance of the sharp
C„N vibration at 2230 cmꢀ1 in their IR spectra. The IR spectrum
of the metal-free phthalocyanine of clamshell type 7 showed
known classical peaks. The peaks at 3303, 1094 and 1035 cmꢀ1
are the characteristic metal-free pc ANH stretching and pyrrole
ring vibration modes. The rest of the spectrum of 7 was similar
Fig. 4. Calculated (B3LYP/6-31G(2d)) relative steric energies of conformations of 5.

_
I. Deg˘irmenciog˘lu et al. / Polyhedron 30 (2011) 1628–1636
1633
to that of 5. Thus, it was enough evidence for the formation of me-
tal-free Pc. In the 1H NMR spectrum of compound 7 the typical
shielding of inner core protons could not be observed due to the
probable strong aggregation. The signals related to aromatic and
aliphatic protons in the macrocyclic moieties and phthalocyanine
skeleton represent the significant absorbance characteristics of
the proposed structure. Furthermore, the MS mass spectrum of
compound 7 showed a molecular parent ion peak at m/z =
1591.84 [M]+, supporting the proposed formula for this compound.
In addition, elemental analysis values was also satisfactory.
The IR spectra of metallophthalocyanines of clamshell type
8–11 were very similar, with the exception of the metal-free
phthalocyanine 7 having an ANH stretching band at 3303 cmꢀ1
due to the inner core. This band were not present in the spectra
of the metallophthalocyanines. The 1H NMR spectra of 10 and 11
could not be determined because of the presence of paramagnetic
cobalt and copper atoms [33]. The 1H NMR spectra of the com-
pounds 8 and 9 were almost identical to those of the metal-free
phthalocyanine 7. Although the aggregation behaviour of the
asymmetric Pcs is lower than symmetric Pcs, some of the signals
of the dyes were broad in their 1H NMR spectrum as a result of
the aggregation of phthalocyanine cores at the considerable high
concentration used for NMR measurements [34]. In the mass
spectra of compounds 8–11, the parent molecular ion peaks were
observed at m/z = 1718.54 [M]+ for 8, 1705.43 [M]+ for 9, 1705.12
[M]+ for 10 and 1714.66 [M]+ for 11, these peaks have verified
the proposed structures.
the time-dependent density functional theory (TD-DFT) at B3LYP
level, providing an accurate description of UV–Vis transitions of li-
gand system. This method was used to compute the 33 sin-
glet ? singlet transitions in vacuum. The related transitions are
listed in Table 1. To better understanding, the three different ben-
zene rings are abbreviated as A, B and C (Fig. 1).
4.1. Interpretation of UV–Vis absorption spectrum of 5 via TD-DFT
calculations
We have completed our study also by theoretical calculations.
The numbering and structure of the studied compound is illus-
trated in Fig. 1. The compound 5 can theoretically exist in 12 struc-
tural forms as follows [47,48]; sEEEs, sEEZs, sZEZs, aEEEa, aEEZa,
aZEZa, sEZEs, sEZZs, sZZZs, aEZEa, aEZZa, aZZZa (Fig. 4). The first
and fifth letters in the labelling denote the orientation of the meth-
oxy group to the C@C double bond (i.e. in case of s(syn) the meth-
oxy group is oriented towards the C@C double bond or in case of
a(anti) the methoxy group is oriented away from the the C@C dou-
ble bond), the second and fourth letters represent the orientation
Table 2
Selected geometric parameters (bond lengths in Å, bond and dihedral angles in
degrees) of the most stable aZZZa conformer and the other ones.
aZZZa Conformer
The other ones
C7AC8 (in Å)
C8AO2
1.385
1.40
between 1.348–1.381
1.371–1.399
1.097–1.111
1.349–1.382
1.079–1.099
1.094–1.10
0
C2AH2
1.115
1.399
1.101
1.114
1.114
1.394
1.379
1.104
1.396
1.402
1.463
120.0
110.39
108.86
116.91
112.23
112.23
120.23
120.43
119.36
118.34
124.91
ꢀ4.31
0.06
C6AC7
C7AH7
3.2. UV–Vis absorption spectra
0
C22AH22
C22AH22
C11AC12
C17AC18
C18AH18
C18AC19
C19AC20
C20ACN
UV–Vis spectra of phthalocyanines show two well-known
0
1.094–1.10
bands as a result of
p ?
p⁄ transitions of the macrocycle moiety.
1.360–1.389
1.357–1.377
1.084–1.102
1.369–1.391
1.376–1.399
1.319–1.411
119.83–119.97
108.68–110.0
108.31–108.80
114.57–116.22
109.84–111.56
109.78–111.54
118.18–120.21
118.19–120.12
117.39–119.25
115.39–118.01
119.97–121.78
3.99–4.31
One around ca. 300 nm is called as the ‘‘B’’ or Soret band, while
the other one at 600–700 nm is called as the ‘‘Q’’ band. These
two bands are present in all kinds of phthalocyanines. The Q band
in metal-free phthalocyanine splits due to D2h symmetry [35]. The
electronic absorption spectrum of compound 7 in dilute chloro-
form solution at room temperature is shown in Fig. 2. The Q band
splits to Qx and Qy, as expected [36]. The splitting Q band was ob-
served at kmax 699 and 662 nm, indicating the structure with D2h
symmetry [36–39].
The UV–Vis absorption spectra of metallophthalocyanines 8–11
in chloroform are very similar, with intense Q absorption bands be-
tween 679 and 672 nm with shoulders at 650–610 nm (corre-
sponds to degenerate D4h symmetry) and B bands at ca. 320 nm.
These results were typical for metal complexes of substituted and
unsubstituted Pcs with D4h symmetry (Figs. 2 and 3) [35,38–43].
O1AC3AC4 (in °)
0
O1AC2AH2
O1AC2AC1
O2AC8AC3
O2AC22AH22
O2AC22AH22
N1AC10AC15
0
00
C
C
19AC20AC20
19AC18AH18
O3AC16AC17
O3AC16AC21
O1AC3AC8AO2 (in °)
O2AC8AC7AH7
N1AC10AC11AH11
0.05–0.54
0.04–4.25
5.36
0
N2AC19 AC19AC18
ꢀ4.25
ꢀ1.11–3.99
O3AC16AC17AH17
O3AC16AC21AH21
2.22
2.11–2.20
4. Computational details
ꢀ2.71
1.99–2.70
The input structures of 5 were optimised using with combina-
tion of PM3 and RHF/3-21G methods [35,36]. Then the obtained
ground-state geometry was optimised in vacuo with the B3LYP/
6-31G(2d) method [35,36] and Becke’s three-parameter hybrid
functional (B3) with the nonlocal Lee–Yang–Parr theoretical corre-
lation (LYP) method [44,45]. The vibrational frequency calculations
were performed for all the studied conformations to check the
structure stabilities that correspond to the minima in the potential
energy surface. All calculations were performed with the GAUSSIAN
03W program package [46]. In calculations, tight converge criteria
was used. By allowing that all the parameters could relax, all the
calculations converged to optimised geometries, which corre-
sponded to true energy minima. On the basis of the optimised
ground state structure, the spectroscopic properties and UV–Vis
absorption calculations in vacuum have been carried out by using
Table 3
Occupancies (e) of natural orbitals (NBOs) and interaction energies (kJ/mol) between
donor–acceptor NBOs in aZZZa conformer calculated at the B3LYP/6-31G(2d) level.
Donor ? acceptor interaction.
Donor
Acceptor
Energy
Occupancy
Lp(2)O1
Lp(1)O1
Lp(2)O2
Lp(1)O2
Lp(2)O3
Lp(1)O3
Lp(1)N1
r⁄(C2AH2)
p⁄(C3AC8)
r⁄(C22AH22
p⁄(C8AC7)
26.31
4.90
25.19
7.10
42.92
4.99
4.48
7.17
3.28
1.923
1.955
1.857
1.961
1.848
1.944
1.972
1.966
1.970
)
r⁄(C21AC20
)
)
p⁄(C16AC17
r⁄(C6AC9)
r⁄(C10AC11)
r⁄(C19AC19
)
0
Lp(1)N2

_
1634
I. Deg˘irmenciog˘lu et al. / Polyhedron 30 (2011) 1628–1636
Fig. 5. The calculated transitions corresponding to experimental spectrum of 5 in B3LYP/6-31G(2d) level (TD-DFT). a denotes first absorption, b denotes second one, c denotes
third one, d denotes fourth one and e denotes fifth one.
around CH@N double bond (including C6AC9ANAC10 dihedral an-
gle), and the third letter corresponds to the variation around the
tion energy obtained from the NBO analysis [51,52], and represents
the estimate of the second-order interaction energy (E(2)). In this
work, we are interested in the interactions between the oxygen/
nitrogen lone-pair orbitals as donors and the antibond-
ing r⁄(C2AH2)/p⁄(C3AC8), r⁄(C22AH22)/p⁄(C8AC7), r⁄(C10AC11),
0
0
central C@C double bond (including C2 AC1 AC1AC2 dihedral an-
gle). According to the calculations at DFT level, the energy of aZZZa
conformer is significantly lower due to the lying at a nearly planar
plane of the phenolic oxygen and methoxy group bonded to the
olefinic carbons and the possibility of the inclusion of the lone
pair/pairs on nitrogen/oxygen frameworks into the conjugation
than those other conformers. In this endeavour, the obtained
course revealed the hyperconjugation in terms of strong delocal-
r⁄(C19AC19 ), and r⁄(C21AC20)/p⁄(C16AC17) orbital teams as recep-
0
tors. The NBO calculations have provided the detailed insight into
the nature of the electronic conjugations in the 12 conformers of
5. The calculated occupancies of natural orbitals and the energies
of interactions between the donor and acceptor orbitals in the most
stable conformational isomer of 5 are collected in Table 3. As can be
seen also from this table, the two lone electron pair orbitals, Lp(1)
and Lp(2) on the oxygen atoms O1, O2 and O3, prove a considerable
decrease of occupancy from the idealised value of 2.0 e. In aZZZa,
three hyperconjugative interactions, the donation of electron den-
sity from the oxygen (O1, O2 and O3) lone pair orbitals with sp-char-
acter, Lp(2)O to a corresponding antibonding orbitals, r⁄(C2AH2),
r⁄(C22AH22) and r⁄(C21AC20), are predominant. The calculated
ization of the p, r and lone pair orbitals involved in it.
The term hyperconjugation was introduced by Mulliken to de-
scribe the interaction the between a multiple bond and a saturated
bond type (first-order hyperconjugation) or between two saturated
groups (second-order hyperconjugation) [49,50]. Hyperconjuga-
tion can be explained as a stabilizing interaction arising from over-
lap of an occupied orbital with an adjacent one containing fewer
electrons. It endeavours to build
p-bond character into bonds hav-
ing only or lone pair character.
r
Lp(2)O1 ? r⁄(C2AH2), Lp(2)O2 ? r⁄(C22AH22
)
and Lp(2)O3 ?
For all conformations, the effect of hyperconjugation can be
illustrated. Especially, in case of aZZZa conformer, while O1 forms
a dihedral angle of ꢀ4.31° O2 donor, O2 forms a dihedral angle of
0.06° H7, N1 forms a dihedral angle of 5.36° H11, N2 forms a dihedral
r⁄(C21AC20) interaction energies are 26.31, 25.29 and 42.92 kcal/
mol, respectively. These transitions cause to an increase of
occupancies of the antibonding orbitals, r⁄(C2AH2), r⁄(C22AH22
)
and r⁄(C21AC20), as shown in Table 3. The known fact from the
usual interactions summarised above, the aZZZa conformer should
be the most stable one [53,54].
angle of ꢀ4.25° C18, and O3 forms a dihedral angle of 2.22° H17(21)
,
respectively, the other whole conformers have a value between
0.04 and 4.31 dihedral angles. In that case, hyperconjugation in-
UV absorption spectrum of 5 was calculated using time-depen-
dent density functional theory (TD-DFT) method based on B3LYP/
6-31G(2d) basis set in order to compare with experimental results.
This strategy leads to an average discrepancy of 2–12 nm between
theoretical and experimental kmax due to several influencing fac-
tors, such as solvent effect and intermolecular interaction, etc.
DFT calculations were carried out in order to know the geometry
of the frontier orbitals of the related compound. According these
0
0
00
creases C8AC7/C8AO2/C2AH2 ; C7AC6/C7AH7C22AH22 =C22AH22
;
C11AC12
;
C18AC19/C19AC20
;
C17AC18/C18AH18/C20AC19/C20ACN
0
bond lengths, and O1AC3AC4/O1AC2AH2 =O1AC2AC1; O2AC8A
0
00
0
C3/O2AC22AH22 =O2AC22AH22
; N1AC10AC15; C19AC20AC20 /C19A
C
18AH18 and O3AC16AC17/O3AC16AC21 bond angles, as
,
summarised in Table 2. Besides of these gains, hyperconjugation
is also quantified in terms of the second-order perturbation interac-

_
I. Deg˘irmenciog˘lu et al. / Polyhedron 30 (2011) 1628–1636
1635
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calculations, the highest occupied molecular orbitals (HOMOs) are
mainly localised on the related oxygen atoms, benzene carbons
(including A, B and C), C„N and CH@N groups. Similarly, the low-
est unoccupied molecular orbitals (LUMOs) are also centred on the
related oxygen atoms, benzene carbons (including A, B and C),
CH@N, C„N, ACH3 and olefinic carbons with their different
contributions.
TD-DFT studies have been very useful in order to assign the
electronic absorption transitions of the compounds. The low-en-
ergy excitations obtained by this method are in good agreement
with the experimental results. According these calculations, the
HOMO is composed of the
p-bonding –2py + pz/2px + py orbital
teams of the benzene rings– A, B and C, nppz and rpx orbitals of
the oxygen atoms O1, O2 and O3, the ppz orbitals of the CH@N
and C„N groups, and px orbitals with non-bonding interactions
of ACH3 and ACH2 groups with small contributions. The HOMOꢀ1
is centred on the same orbital teams with their different density.
The HOMOꢀ2 and HOMOꢀ3 are also fragments based on the same
orbital teams with their different density. The HOMOꢀ4 and
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HOMOꢀ5 are located on the 2py + pz/2px + py orbitals with
metry of B and C moieties, ppz orbitals of the CH@N and C„N
groups and similarly related –p orbitals with same symmetry/en-
p-sym-
p
[20] N. Nombona, E. Antunes, T. Nyokong, Dyes Pigm. 86 (2010) 68.
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ergy of the O2 group with small contributions [35,55].
The LUMO and LUMO+1 are also a set of quasi degenerated orbi-
tals. These orbitals show a predominant character of the C moiety
(including 2py + pz– character), CH@N/C„N groups (including
r⁄ p⁄ character) and oxygen atom O3 (including ppꢂz-character)
A
combinations. On the other hand, the LUMO+2 is composed of orbi-
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r
/
⁄ p⁄-symmetry of the A annular, C„N/CH@N groups,
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olefinic carbons C@C and oxygen atom O1. Similarly, the LUMO+3
has an important contribution of the A ring, CH@N/CH@N groups,
ACH2 and O1 atoms. The intensity of these transitions has been as-
sessed from the oscillator strength (f). All these transitions are of
_
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Inc., New York, 1996, pp. 1–18.
intra-ligand n(r p
) ? r⁄ and n( ) ? p⁄ charge transfer origin (LLCT)
transitions [56,57]. The involved orbitals in these transitions are
presented in Fig. 5 and the most relevant electronic transitions
are present in Table 1.
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_
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5. Conclusion
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_
[35] K. Serbest, I. Deg˘irmenciog˘lu, Y. Ünver, M. Er, C. Kantar, K. Sancak, J.
In this paper, we have reported on the preparation of a new type
of an olefinic centred metal free and metallophthalocyanines (Zn,
Ni, Co and Cu) of clamshell type. In the first stage, substituted
Schiff Base analogue was obtained from condensation of 1 and 2
with no solvent. Then, compound 5 was synthesized from a mix-
ture of 3 and 4 (2:1) in the presence of DMF/K2CO3 as key structure
to give expected pcs. In the final stage, metal free and metallopht-
halocyanines of clamshell type were synthesized by the interaction
of diphthalonitrile 5 with excess of phthalonitrile 6 in DMAE/DBU
and corresponding metal salts. The preparations of the new prod-
ucts are supported by elemental analysis, IR, UV–Vis, 1H/13C NMR
and mass spectra.
Organomet. Chem. 692 (2007) 5646.
_
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Acknowledgement
This work was supported by The Research Fund of Karadeniz
Technical University, Projects No: 2007.111.002.9 and 2010.111.
002.3 (Trabzon/Turkey).
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