The new ball-type zinc phthalocyanine with S[sbnd]S bridge; Synthesis, computational and photophysicochemical properties

Article abstract of DOI:10.1016/j.jphotochem.2019.112287

In this study, the starting compound 4,4′-disulfanediyldiphthalonitrile (1) and its ball-type zinc phthalocyanine (2) were synthesized and characterized by standard spectroscopic methods. The molecular structure and supramolecular dynamics of the compound (1) have been investigated by the analysis of the single crystal X-ray diffraction data. To further understand the intermolecular interactions of compound (1), the Hirshfeld surface analysis has been carried out. The compound (1) and (2) were investigated by quantum chemical calculations. Their quantum chemical parameters such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), chemical hardness were performed by B3lyp, HF, M062x method. The ΔG values of the compound (1) and (2) were calculated by using the obtained results. The calculated Infrared spectroscopy, Nuclear Magnetic Resonance, and UV–vis spectra of the compounds were investigated. In addition, photophysical (fluorescence quantum yields) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of newly synthesized ball-type zinc phthalocyanine (2) were investigated in dimethyl sulfoxide (DMSO) solutions. We obtained very high singlet oxygen quantum yields as 0.89, suggesting its potential as photosensitizer in PDT treatment.

Full text of DOI:10.1016/j.jphotochem.2019.112287

Journal Pre-proof
The New Ball-Type Zinc Phthalocyanine with S-S Bridge; Synthesis,
Computational and Photophysicochemical Properties
Ahmet T. Bilgi c¸ li, Hayriye Gen c¸ Bilgi c¸ li, Arma g˘ an Gu¨nsel,
HasanPi s¸ kin, Burak Tu¨zu¨n, M. Nilu¨fer Yarasir, Mustafa Zengin
PII:
S1010-6030(19)31297-3
DOI:
https://doi.org/10.1016/j.jphotochem.2019.112287
JPC 112287
Reference:
To appear in:
Journal of Photochemistry & Photobiology, A: Chemistry
Received Date:
Revised Date:
Accepted Date:
30 July 2019
2 December 2019
3 December 2019
Please cite this article as: Bilgi c¸ li AT, Bilgi c¸ li HG, Gu¨nsel A, HasanPi s¸ kin, Tu¨zu¨n B, Nilu¨fer
Yarasir M, Zengin M, The New Ball-Type Zinc Phthalocyanine with S-S Bridge; Synthesis,
Computational and Photophysicochemical Properties, Journal of Photochemistry and amp;
Photobiology, A: Chemistry (2019), doi: https://doi.org/10.1016/j.jphotochem.2019.112287
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The New Ball-Type Zinc Phthalocyanine with S-S Bridge; Synthesis,
Computational and Photophysicochemical Properties
a
a
a
b
Ahmet T. Bilgiçli *, Hayriye Genç Bilgiçli , Armağan Günsel , HasanPişkin ,
c
a
a
Burak Tüzün , M. Nilüfer Yarasir , Mustafa Zengin
a
Sakarya University, Department of Chemistry, Sakarya, Turkey,
Gebze Technical University, Department of Physics, 41400 Gebze, Kocaeli, Turkey
Cumhuriyet University, Department of Chemistry, Sivas, Turkey
b
c
Graphical abstract

Research Highlight

Synthesis and characterization of 4,4'-disulfanediyldiphthalonitrile as ligand and their
ball-type zinc phthalocyanine


The single crystal X-ray diffraction experiment and the Hirshfeld surface analysis.
Quantum chemical calculations of 4,4'-disulfanediyldiphthalonitrile and their ball-type
zinc phthalocyanine.

The ball-type zinc phthalocyanine with high singlet oxygen quantum yield as 0,89.
Abstract
In this study, the starting compound 4,4'-disulfanediyldiphthalonitrile (1) and its ball-type
zinc phthalocyanine (2) were synthesized and characterized by standard spectroscopic
methods. The molecular structure and supramolecular dynamics of the compound (1) have
been investigated by the analysis of the single crystal X-ray diffraction data. To further
understand the intermolecular interactions of compound (1), the Hirshfeld surface analysis has
been carried out. The compound (1) and (2) were investigated by quantum chemical
calculations. Their quantum chemical parameters such as highest occupied molecular orbital
(HOMO), lowest unoccupied molecular orbital (LUMO), chemical hardness were performed
by B3lyp, HF, M062x method. The ΔG values of the compound (1) and (2) were calculated
by using the obtained results. The calculated Infrared spectroscopy, Nuclear Magnetic
Resonance, and UV-Vis spectra of the compounds were investigated. In addition,
photophysical (fluorescence quantum yields) and photochemical (singlet oxygen generation
and photodegradation under light irradiation) properties of newly synthesized ball-type zinc
phthalocyanine (2) were investigated in dimethyl sulfoxide (DMSO) solutions. We obtained
very high singlet oxygen quantum yields as 0.89, suggesting its potential as photosensitizer in
PDT treatment.
Keywords: Ball-type phthalocyanine, single crystal, Quantum Chemical Calculation,
Photochemical and Photophysical

*
Authors to whom correspondence should be addressed [Tel: +90(264)2957116; E-mail address:
abilgicli@sakarya.edu.tr
1
. Introduction
Phthalocyanines have been extensively investigated as functional materials in scientific
research due to their important chemical, biological and physical properties in recent years
[1]. The extraordinary chemical and physical features of phthalocyanines are due to the
delocalized 18-π electron system [2, 3]. Thanks to the delocalized 18-π electron systems,
phthalocyanines are interesting for many application areas such as gas sensors [4], chemical
sensor [5], liquid crystals [6], optical disks [7], catalysts [8], optoelectronics [9],
electrochromic devices [10], photovoltaic cell [11], and photodynamic therapy [12].
The cancer is one of the most dangerous diseases of our day. Chemotherapy, radiotherapy,
surgery and photodynamic therapy (PDT) are common technics used in the treatment of
cancer. Compared to the surgery, chemotherapy and radiotherapy methods, photodynamic
therapy has got some advantages and has been thought as a more promising method in the
treatment of cancer. Photodynamic therapy is based on the transformation of light energy into
chemical energy through a photosensitizer and singlet oxygen generation to kill cancer cells
[13, 14].
Ball-type phthalocyanines are one of the macrocyclic compounds which have increasing
importance in recent years. In these kinds of compounds, the two phthalocyanine monomers
are generally bridged to each other with benzene derivatives from the peripheral positions of
the benzene rings. In this study, the two phthalocyanine monomers are linked by S-S bridges
instead of benzene derivatives unlike others. The spectroscopic, electrochemical,
photochemical and photopysical properties of ball-type phthalocyanines are different from
phthalocyanine monomers [15-17]. Some studies on ball-type phthalocyanines have been
published after being synthesized in 2002 for the first time [18]. But, photophysical and
photochemical properties of ball-type phthalocyanines are still limited [19-21].
In this present work, 4,4’-disulfanediyldiphthalonitrile (1) as ligand and their ball-type zinc
phthalocyanine (2) were prepared. In order to reveal the molecular structure and the bonding
dynamics of the supramolecular structure for the compound (1), the single crystal X-ray
diffraction experiment and the Hirshfeld surface analysis have been done. The spectral,

structural and computational properties of compound (1) and (2) were performed. Then, we
have investigated the photochemical (singlet oxygen quantum yields and photodegradation
quantum yields) and photophysical properties (fluorescence quantum yields) of ball-type zinc
phthalocyanine (2). We expect that ball-type zinc phthalocyanine (2) was a mixture of
isomers of the dimers with the thio groups in different positions. The separation of possible
structural isomers of phthalocyanines is very difficult by column chromatography. Hence, no
attempt was made to separate the isomers of the ball-type zinc phthalocyanine (2). The
obtained photochemical and photophysical results were a mixture of isomers.
2
2
. Experimental
.1. Materials and Methods
The used all solvents and chemical compounds such as 4-nitrophthalonitrile, SnCl
acetate, chloroform(CHCl ), dichloromethane (CH Cl ), dimethylformamide(DMF),
ethanol(EtOH), methanol(MeOH), dimethyl sulfoxide(DMSO), tetrahydrofuran(THF),
hydrochloric acid (HCl), sodium nitrite (Na ), 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU) were
purchased from commercial suppliers such as Merck, Fluka, Aldrich and Alfa Aesar. All
reactions were carried out under a dry N atmosphere. The structure of the compounds was
analyzed with common spectroscopic technics such as fourier-transform infrared spectroscopy
2
, zinc(II)
3
2
2
S
2 2
2
1
13
(
FT-IR), proton nuclear magnetic resonance ( H-NMR), carbon nuclear magnetic resonance ( C-
NMR), ultraviolet and visible light (UV-Vis) spectral data, and matrix-assisted laser
desorption/ionization-time of flight mass spectrometer (MALDI-TOF MS). FT-IR spectra of the
compounds were taken by Perkin Elmer Spectrum Two FT-IR Spectrometer. UV-Vis spectra
of the compounds were recorded by Agilent Model 8453 diode array ultraviolet-visible
spectrophotometer. Fluorescence properties were performed by Hitachi S-7000 fluorescence
spectrophotometer. H-NMR and 13C-NMR spectra were recorded on a Bruker 300
spectrometer instruments.
1
2
.2. Synthesis of 4,4'-disulfanediyldiphthalonitrile (1)
4
-nitrophthalonitrile was converted to 4-aminophthalonitrile in the presence of hydrochloric
acid and Tin (II) chloride according to literature [22]. The diazonium salt of obtained product
was prepared with addition of sodium nitrite solution in hydrochloric acid and then 4,4'-

disulfanediyldiphthalonitrile (1) was obtained in the presence of sodium sulfide according to
-1
literature (Scheme 1) [23]. C16
H
6
N
4
S
2
(318,38 g.mol ) elemental analysis: calculated (C,
1
6
0.36; H, 1.90; N, 17.60) found (C, 60.41; H, 1.98; N, 17.11). H NMR (300 MHz, in DMSO)
δ ppm: 8.01 (dd, 1H (H-4 and H-14), Jo= 8.20 Hz, Jm= 1.5 Hz), 8.09 (d, 1H (H-3 and H-13)),
1
3
8
.33 (d, 1H (H-6 and H-10)). C NMR (75 MHz, in DMSO) δ ppm: 113.7 (C-2, C-12), 116.0
C-1, C-11), 116.3 (C-15, C-19, C-21, C-23), 131.6 (C-6, C-10), 131,8 (C-3, C-13), 135.0 (C-
(
4
2
4
, C-14), 143.5 (C-5, C-9). UV-Vis (in DMSO) λmax: 233nm and 277 nm.
.3. Synthesis of ball-type zinc phthalocyanine (2)
,4'-disulfanediyldiphthalonitrile (150 mg, 0.47 mmol) in 2-dimethylamino-ethanol (DMAE)
3
(
5 mL) and DBU (0.05 cm ) was heated at 160 °C for 30 minutes under N
2
atmosphere. The
anhydrous zinc (II) acetate (0.030 g, 0.22 mmol) was added to the reaction. The reaction
mixture was stirred for 12h (Scheme 2). After the reaction was completed, reaction mixture
was cooled to room temperature. First of all, the reaction mixture was precipitated with
hexane and then the solid product was washed with water, acetonitrile and MeOH in order to
remove impurities, respectively. Further purification was made by column chromatography
with CHCl
2) was obtained with % 13 yields (20 mg). The novel ball-type zinc phthalocyanine (2) is
well soluble in DMF and DMSO and is partially soluble in THF, CHCl and CH Cl . The
chemical formula of (2): C64 Zn
, calculated molecular weight: 1404.32 g.mol-1
Table S1). Elemental analysis: calculated (C, 54.74; H, 1.72; N, 15.96), found (C, 55.01; H,
3
-MeOH (20/2 v/v) as eluent. After the purification, ball-type zinc phthalocyanine
(
3
2
2
H
24
16
N S
8
2
(
1
1
.68; N, 16.13), H-NMR (300 MHz, in DMSO) δ ppm: 7.96–8.15 (16H, Pc–H), 8.30–8.38
(8H, Ar–H). UV-Vis (in DMSO): λmax, (log ε); 687 nm (4.81) (Q-Band) and 355 nm (4.85)
(
B-Band). MALDI-TOF-MS, (Dithranol): m/z: 1404.89 [M+H]+.
2
.4. X-ray data collection and refinement for the 4,4'-disulfanediyldiphthalonitrile (1)
The HKL data of the 4,4'-disulfanediyldiphthalonitrile (1) has been collected by a Bruker
APEX II Quazar three-circle diffractometer with mono-chromated Mo-K radiation (λ=
.71073 Å). In the experiment done at 172 K, a colorless crystal with a size of 0.494 × 0.177
α
0
×
0.086 mm has been chosen. Totally 10375 reflections have been observed. Among them,
1
339 reflections were independent and 1318 reflections were I > 2σ (I). The molecular
structure of compound 4,4'-disulfanediyldiphthalonitrile (1) has been solved by using the

intrinsic phasing in SHELXT and then refined by full-matrix least-squares refinements on F2
using SHELXL in Olex2 program. The table 1 presents the crystallographic information, data
collection and the summary of the final refinement results for the 4,4'-
disulfanediyldiphthalonitrile (1).
2
2
.5. Photophysical and Photochemical Parameters
.5.1. Fluorescence quantum yields
Fluorescence quantum yield (Φ ) of the novel ball-type zinc phthalocyanine (2) was determined
F
with the comparative method using by the following equation (1) in DMSO at room
temperature [24, 25].
F.Aꢀꢁꢂ.n2
Φ = Φ (Std)
(1)
F
F
Fꢀꢁꢂ ꢃ. ꢄ
2
ꢀ
ꢁꢂ
In this equation, Φ
F
is the quantum yield of the compound (1), Φ
F
(Std) is the quantum yield
of the reference compound, F and FStd are the areas under the fluorescence emission curves of
the novel ball-type zinc phthalocyanine (2) and unsubstituted zinc phthalocyanine as a standard,
respectively. Absorbance of the reference and sample compounds are AStd and A,
respectively. 푛 and 푛ꢅ are the refractive indices of solvents used for the sample and
ꢅ
푆푡푑
standard, respectively. The quantum yield of the reference compound (unsubstituted zinc
phthalocyanine) was used as Φ = 0.20 according to literature [26].
F
2
.5.2. Singlet oxygen quantum yields
The singlet oxygen quantum yield of novel ball-type zinc phthalocyanine (2) was determined in
air by using the following equation in DMSO at room temperature; in the equation (2), zinc
phthalocyanine as a reference and DPBF as chemical quencher were used.
Std
abs
Std
R .Iabs
R .I
Std
ΦΔ  ΦΔ
(2)

Std
ΦΔ
In this equation,
is the singlet oxygen quantum yield of reference sample. The singlet
oxygen quantum yield of the reference compound (unsubstituted zinc phthalocyanine) was
Std
ΦΔ
used as
= 0.67 in DMSO according to literature) [26]. R and RStd are the photobleaching
rates of DPBF in the presence of the novel ball-type zinc phthalocyanine and unsubstituted
zinc phthalocyanine as a reference. Iabs and Iꢆꢇꢈ are absorption rates of light in the presence of
abs
the novel ball-type zinc phthalocyanine and unsubstituted zinc phthalocyanine as a reference.
The solutions containing DPBF prepared in dark environment and the degradation of DPBF at
4
17 nm was monitored after each 5s irradiation [27, 28]. The absorption band of DPBF at 417
nm reduced after the light irradiation [28].
2
.5.3. Photodegradation quantum yields
The photo degradation quantum yield of novel ball-type zinc phthalocyanine was determined
by using the following equation (3);
(C0
 C
t
).V. N
A
Φd 
Iabs.S. t
(3)
In this equation, C
0
is the concentration of novel ball-type zinc phthalocyanine before the
is the
irradiation and C is the concentration after the irradiation. V is the reaction volume, N
t
A
Avogadro’s constant, S is the irradiated cell area, “t” is the irradiation time, Iabs is the overlap
integral of the radiation source light intensity and the absorption of the samples [28].
3
3
. Results and discussion
.1. Synthesis and characterization
The structure of synthesized compounds was verified by using some spectroscopic methods
such as UV-Vis, FT-IR, H-NMR, 13C-NMR, elemental analysis and MALDI-MS. The
theoretically calculated IR, NMR, and UV-Vis spectra of the starting compound (1) and their
ball-type zinc phthalocyanine (2) were investigated and the obtained parameters were
compared with experimental values. All the obtained results are compatible with the expected
compound structures.
1

4
,4'-disulfanediyldiphthalonitrile (1) was synthesized from 4-nitrophthalonitrile as shown in
Scheme 1. 4-nitrophthalonitrile was converted to 4-aminophthalonitrile and then 4,4'-
1
disulfanediyldiphthalonitrile was obtained. FT-IR and H-NMR results supported the expected
compound structures.
FT-IR spectra of 4-nitrophthalonitrile and 4-aminophthalonitrile were given in Fig. S1. The
-1
characteristic -C≡N stretching peaks belong to the dinitriles shifted from 2243 cm to 2214
cm-1 after the conversion reaction of 4-nitrophthalonitrile to 4-aminophthalonitrile. The
-1
-1
characteristic peaks at 1532 cm and 1350 cm related to nitro groups were disappeared and
-1
-
stretching vibrations corresponding to primary amino groups at about 3488 cm and 3358 cm
1
-1
-
were appeared. The characteristic -C≡N stretching peaks shifted from 2214 cm to 2233 cm
1
-1
-1
-1
and aromatic CH stretching peaks were observed at 3094 cm , 3060 cm and 3019 cm
Fig. S2). The novel ball-type zinc phthalocyanine (2) was synthesized with
(
cyclotetramerization reaction of 4,4'-disulfanediyldiphthalonitrile (1). After the reaction,
-1
characteristic -C≡N stretching peak at 2233 cm disappeared. This supported the formation of
the phthalocyanine (2) (Fig. S2).
UV-Vis spectroscopy is a very useful technique for the characterization of phthalocyanines.
Because phthalocyanines have some characteristic peaks in electronic absorption spectra.
This characteristic peaks are that 650-700 nm regions (Q-band) arising from the π–
π*transition and 300-400 nm regions (B-band) arising from deeper π–π*transitions.
Especially, Q band regions provides information about whether metallophthalocyanines or
metal-free phthalocyanines. The electronic absorption spectra of novel ball-type zinc
phthalocyanine (2) were recorded in DMSO and DMF. The Q-band absorption arising from the
π–π*transition of compound (2) was appeared as a single band with high intensity at 688 nm
in DMSO and 689 nm in DMF. The B-band absorption arising from the deeper π–π*transition
of compound (2) was appeared at 352 nm in DMSO and 351 nm in DMF.
One of the common spectroscopic techniques used for characterization is mass spectroscopy.
Thus, mass spectroscopy was used for characterization. The molecular ion peak of ball-type
+
zinc phthalocyanine (2) was observed at m/z: 1404.898 [M] in the MALDI-TOF-MS
(Dithranol as matrix) (Fig. S3).
1
In the H-NMR spectrum of 4,4'-disulfanediyldiphthalonitrile (1), the aromatic protons
appeared at between δ:7.997 and 8.331 ppm. H-4 shows a doublet of doublets at 8.01 ppm.
The interaction constants were calculated as 8.20 Hz for ortho (with H-3) and 1.5 Hz for meta
(with H-6). H-3 shifted as a doublet at 8.09 ppm, and H-6 shifted as a doublet at 8.33 ppm
1
3
(
Fig. S4). In the C-NMR spectrum of 4,4'-disulfanediyldiphthalonitrile, the related carbon

peaks appeared at δ: 113.7 (C-2, C-12)4, 116.0 (C-1, C-11)4, 116.3 (C-15, C-19, C-21, C-
2
3)4, 131,.6 (C-6, C-10)1, 131,8 (C-3, C-13)77, 135.20 (C-4, C-14), 143.5 (C-5, C-9)49 ppm
1
(
Fig. S5). In the H-NMR spectrum of the novel ball-type zinc phthalocyanine (2), the
aromatic protons were obtained in a higher area and broader compared to compound (1) due to
the face to face interaction of two monomers in ball-type zinc phthalocyanine (2).
3
.2. Results of X-ray diffraction experiment for the 4,4'-disulfanediyldiphthalonitrile (1)
The XRD experiment proved that an orthorhombic (P2
1
1
2 2) single crystal has formed with the
unitcell parameters of 푎 = 1ꢉ.300ꢉ Å , 푏 = 1ꢉ.9658 Å, 푐 = 4.7080 Å. There are two
molecules in the unitcell. The Fig. 1(a) presents the asymmetric unit of the compound (1),
which is the half of a molecule. In the Fig. 1(b), a completed arrangement is given with the
atomic labels and gravity centres for five/six-membered rings. For clarity, the hydrogen atoms
were not labelled in the figure, but they have been labelled as the same number with carbon
atom labels which they are bonded (like C6—H6).
In the completed fragment of the molecule, a strong intra-molecular S1a···H6 (or/and
S1···H6a) interaction has been observed with an interaction distance of 2.72 Å which is ~%10
shortened compared to their Van der Waals radii (1.80 Å and 1.20 Å, respectively). Thus, two
five-membered rings (S1a—S1—C1—C6—H6 and S1—S1a—C1a—C6a—H6a) have
formed as a planar conformation with an RMS deviation of 0.0948 Å. The dihedral angle
between these two planes is 75.1° and the Cg2···Cg2a distance is 2.30 Å. Also, the six-
membered rings exhibit a perfect planar conformation with an RMS deviation of 0.0034 Å.
The dihedral angle between the six-membered ring planes is 86.5° and the Cg1···Cg1a
distance is 5.681 Å. The selected bond geometries for the 4,4'-disulfanediyldiphthalonitrile (1)
have been presented in table S2.
The supramolecular structure of the 4,4'-disulfanediyldiphthalonitrile has been stabilized by
the domination of Cg···Cg, Cg···N, Cg···S, one strong D—H···A (C6—H6···N1= 2.54 Å)
and one week D—H···A (C3—H3···N2=2.72 Å) interactions. As shown in Figure S6, the
C—H···N interactions provide the stability along the ab plane while the other interactions
provide the stability along the c-axis. These interactions have been listed in table S3 and
table S4. The unitcell presentation through the view for (100), (001), (010), (011) and (101)
of the compound (1) were given in (Fig S7- Fig S11), respectively.
3
.3. Results of Hirshfeld surface analysis for the 4,4'-disulfanediyldiphthalonitrile (1)

To further understand the intermolecular interactions of the 4,4'-disulfanediyldiphthalonitrile
1), the Hirshfeld surface analysis has been done. This is a method that can show
(
intermolecular interactions in a powerful way and also it supplies visual results. The figure
S12 presents the Hirshfeld surfaces of the 4,4'-disulfanediyldiphthalonitrile in three different
angles of view with d-norm, shape index and curvedness modes. The red zones in d-norm and
shape index, which are shown by black arrows in the figure, indicate the strongest D—H···A
and Cg···X (X: S1, N1) interactions, respectively.
The D—H···A bonds have already been presented in figure S6. The Cg···X bonds have been
presented in figure 2 (along c-axis). The sulfur atoms of the top molecule conform almost top
of the midpoint of the six-membered rings of the bottom molecule. Similarly, the half of the
nitrogen atoms of bottom molecule conforms to midpoint of six membered rings of top
molecule.
According to Hirshfeld surface analysis, the percentages of intermolecular interactions are
given as follows: C···C= % 8.6, C···H= %11.5, C···N= %11.2, C···S= %11.5, N···H= %46,
N···N= %1.6, N···S= %3.8, S···H= %1.2, H···H= %4.6. All of these interactions have been
presented in fingerprint plots (di: internal distance, de: external distance) in Figure S13.
3
.4. Calculation Results
It is well known that theoretical studies are used to investigate the activity of molecules and
chemical reactions. The chemical parameters obtained by quantum chemical calculations are
used to describe them. In this present work, the results obtained from the quantum chemical
parameters are interpreted by comparing the activities of the molecules in table S5 and S6.
HOMO and LUMO values of the studied molecules should be known for interpret these
results. The most important parameter used to compare the activity of molecules is HOMO
energy value, which is demonstrates the electron-donating ability of the organic and inorganic
molecules [29-31].
HOMO and LUMO energy values are the most widely used parameters to compare the
chemical activity of organic and inorganic molecules [32, 33]. In figure 3, the optimized state
of the 4,4'-disulfanediyldiphthalonitrile (1) is shown in the first picture; the second picture has
a HOMO representation of the 4,4'-disulfanediyldiphthalonitrile (1). In this illustration, it is
seen that HOMO orbitals are formed on which atoms. In the third picture, the 4,4'-
disulfanediyldiphthalonitrile (1) have LUMO representation. In this picture, it is seen on

which atoms LUMO orbitals are formed. In the last picture, the electron distribution of the
,4'-disulfanediyldiphthalonitrile (1) is shown [29].
4
Quantum chemical parameters of molecules are calculated by using HOMO and LUMO
energy values of molecules [33, 34]. These quantum chemical parameters are
electronegativity (χ), chemical hardness (η) and global softness (σ), which is related to
HOMO and LUMO energy values. These parameters are used to compare chemical activities
of molecules and measure interactions across metal atoms.
In figure S14, the structure optimized for the metal complex consisting of a combination of
ligand molecule and Zn metal is shown from different angles. In figure 4, The HOMO,
LUMO and electrostatic potentials of the metal complex obtained as a result of the
optimization are shown. 4 different isomers were formed by the combination of ligands. The
structural forms of these formed isomers are shown in figure 4. The energy values of each
c
isomer were calculated. Looking at the energy values, the isomer (2 ) was found to be more
stable than the others (Table S7).
The Gibbs free energy (∆퐺) was calculated by using the equation below:
∆
퐺 = 퐸푀−퐿ꢊ표푚푝푙푒푥푒 ꢋ (퐸푀2+ ꢌ 4 ∑ 퐸퐿푖푔ꢍꢎ푑
)
(4)
where 퐸푀−퐿ꢊ표푚푝푙푒푥푒 is the sum of the electronic and thermal free energies of the metal-
complex, 퐸퐿푖푔ꢍꢎ푑 is the sum of the electronic and thermal free energies of the ligand and
퐸푀2+ is the sum of the electronic and thermal free energies of the metal ion. The Gibbs free
energy (∆퐺) value of the studied complex is given in table S8. This value was negative in the
calculations. A negative value indicates that the reaction is spontaneous.
3
.4.1. NMR spectroscopy
Nuclear Magnetic Resonance (NMR) spectroscopy is one of the most important methods used
to analyze the structure of molecules. NMR spectroscopy is used for the illumination of
covalent compounds. It is based on the measurement of carbon and hydrogen atoms in the
molecule that are stimulated to the rotational energy levels by the absorption of
electromagnetic radiation in the radio frequency range. The experimental and theoretical
NMR values of the studied molecule were determined. These theoretical calculations of

studied molecules were calculated using the gauge-independent atomic orbital (GIAO)
method [35]. The atoms in the studied molecules are labeled as shown in the figure S15. The
1
13
experimental and theoretical H and C NMR chemical shift values are given in table S9 of
1
13
studied molecule. The experimental and theoretical H and C NMR values of this molecule
were calculated by the effect of atomic and atomic groups around the atoms [36, 37]. In this
study, the theoretical calculation of carbon and hydrogen atoms in the molecule was carried
out by using the basis set of HF / 6-31 ++ g. The values obtained as a result of the theoretical
calculations were plotted to compare with the experimental values in figure S16. In the drawn
2
graph, the theoretical values against the experimental values were plotted and R values were
2
2
obtained. These R values were 0.9876 in gas phase and 0.9919 in DMSO phase. These R
values are about 1, which is a very good result. The high R values indicate that these values
are reliable. Considering the results obtained as a result of theoretical studies, it is seen that
the carbon atoms in the aromatic ring when they look at chemical shift values are in the range
of 120-144 ppm. However, the chemical shift values of aliphatic carbon atoms are in the
range of 108-109 ppm. On the other hand, the chemical shift values of hydrogen atoms in the
aromatic ring are observed to be in the range of 8.53-9.00 ppm.
3
.4.2. UV-Vis spectroscopy
Ultraviolet and visible light (UV-Vis) absorption spectroscopy is a measure of the reduction
of a beam after it has passed through a sample or reflected from a sample surface. UV-Vis
spectrum of ligand is calculated at hf/6-31++g level in gas (ε=1), chloroform (ε=4.711),
methanol (ε=32.613), dimethyl sulfoxide (ε=46.826), water (ε=78.355), n-methyl formamide-
mixture (ε=181.56) phase in figure S17. Otherwise, UV-Vis spectrum of metal complex are
calculated at same level only in gas phase in figure 5. In the spectrum of UV-Vis obtained, it
is examined how electronic transitions occurring in studied ligands are affected in different
solvents. In these investigations it has been seen that as the dielectric constant of the solvent
increases, the absorbed wavelength increases [38, 39]. When the UV-Vis spectrum of the
ligand and metal complex is examined, it is seen that there are generally two basic peaks. At
these basic peaks, it is assumed that n → π* and π → π* are electronic transitions.
3
.4.3. IR spectroscopy

Infrared spectroscopy involves the interaction of infrared radiation with studied molecules. It
covers a range of techniques and method, mostly based on absorption spectroscopy. As with
all spectroscopic techniques, it can be used to identify and study chemicals. One of the most
important methods used to identify the structures of molecules from the IR spectra of ligand
and metal complexes. IR spectra of ligand and metal complexes are calculated hf/6-31g (d, p)
level in gaussian. IR spectrum values of the studied ligand and metal complexes were
obtained by using VEDA software [40, 41]. IR spectrum peaks of the studied ligand and metal
complexes are given in table S10. The two spectra obtained from theoretical and
experimental studies are given in figure S18. The red colored spectrum was obtained from
theoretical studies, while the blue spectrum was obtained from experimental studies. When
compared the theoretical and experimental spectra, it is seen that there are great similarities in
the two spectra. The main reason for differences between the spectra are that the theoretical
studies are in the gas phase and do not contain experimental inputs.
3.5. Aggregation Studies
Phthalocyanine complexes are known to exhibit aggregation behavior due to the -electron system.
Aggregation behaviors of phthalocyanines can be differing with solvent, concentration,
temperature and bulk functional group. The formation of aggregates decreases the Q-band intensity
of phthalocyanines and leads to fluorescence quenching and accordingly, decreased singlet oxygen
yield. Thus, the synthesis of phthalocyanines that are not aggregating or showing low aggregation
is important for photodynamic therapy applications.
The aggregation behavior of novel ball-type zinc phthalocyanine (2) was investigated by UV-Vis
spectroscopy in DMSO (Figure S19). Figure S19a exhibits the UV-Vis spectrum of the ball-type
zinc phthalocyanine (2) at different concentrations in DMSO. When the concentration of novel
ball-type zinc phthalocyanine (2) was increased, the Q band intensity increased. No new band
formation was observed due to the aggregated species. Similarly, the new band formation was not
observed in transmittance spectra (Figure S19b). Aggregation behaviors of compound (2) were
also investigated by derivative spectra. It is well known that derivative spectrum gives much
detail information about the spectrum. First derivative spectrum of absorption band gives
cross over point as positive maxima and negative minima (Figure S19c). Second derivative
spectrum is characterized by two satellite maxima and an inverted band of which the
minimum corresponds to the λ max of the fundamental band (Figure S19d). No new band
formation was observed when the concentration was increased in the first and second derivative

spectra of ball-type zinc phthalocyanine (2) as being in the absorbance and transmittance spectra.
The obtained all figures supported that novel ball-type zinc phthalocyanine (2) did not aggregate
in DMSO.
3
3
.6. Fluorescence measurements
.6.1. Fluorescence spectra and fluorescence quantum yields
Fluorescence properties of novel ball-type zinc phthalocyanine were performed in DMSO at
room temperature. Figure 6 exhibits the absorption, excitation and emission spectra of the
novel ball-type zinc phthalocyanine (2) in DMSO. The absorption, excitation and emission
spectral data of the compound (2) was given in Table 2. The excitation and absorption spectra
of the compound (2) are similar and they show the same Q-band maxima. This is indicating
that the nuclear configurations of the ground and excited states are similar and not affected by
excitation in DMSO [42, 43]. However, the absorption spectrum is slightly broader than the
excitation and emission spectrum due to aggregation in the former [19-21]. The fluorescence
emission spectra of the compound (2) are mirror images of the excitation spectra. The
observed Stokes shift of novel ball-type zinc phthalocyanine (2) is 12 nm. The fluorescence
quantum yield (Φ
F
) of novel ball-type zinc phthalocyanine (2) was studied in DMSO. The
fluorescence quantum yield (Φ
F
) value of the compound (2) is 0.09 (table 2). This value is low
compared to unsubstituted zinc phthalocyanine or mono type substituted zinc phthalocyanines. It
may be suggested that is due to the face to face interaction of two monomer in ball-type
phthalocyanines. Energy gap between the triplet state and singlet state may decrease due to face to
face interaction of two monomer in ball-type phthalocyanines and reduce the formation of singlet
state. This causes a decrease in fluorescence. Thus, the fluorescence quantum yield (Φ
ball-type zinc phthalocyanine is low with 0.09 value compared to other zinc phthalocyanines
19-21].
F
) of novel
[
3
.6.2. Singlet oxygen quantum yields
Singlet oxygen quantum yield (Φ
∆
) of the novel ball-type zinc phthalocyanines (2) was
determined by using equation 2 in DMSO at room temperature and listed in table 2. 1, 3-

diphenylisobenzofuran (DPBF) was used as singlet oxygen quencher. Figure 7 shows that
spectral changes of the novel ball-type zinc phthalocyanine with the disappearance of the peak
at 417 nm related to 1,3-diphenylisobenzofuran (DPBF) by using UV-Vis spectroscopy.
During the disappearance of peak at 417 nm, no change was observed in the Q band intensity
of the novel ball-type zinc phthalocyanines (2). This indicates that the novel ball-type zinc
phthalocyanines (2) did not decompose in the presence of DPBF. The Φ
type zinc phthalocyanines (2) is 0.89 in DMSO solution. This value is higher than
unsubstituted zinc phthalocyanine (Φ = 0.67 from Ref [44]). An ideal photosensitizer must be
∆
value of novel ball-
∆
having high singlet oxygen quantum yield for the use in photodynamic therapy treatment. The
novel ball-type zinc phthalocyanine (2) with 0.89 singlet oxygen quantum yield is potential
candidate for the photodynamic therapy treatment of cancer.
3.6.3. Photodegradation quantum yields
Photodegradation is a process that shows the stability of photosensitizer compounds under
light. It is important to determine the stability of the photosensitizer agent to be used in
photodynamic therapy applications. The photodegradation stability of the novel ball-type zinc
phthalocyanine was performed in DMSO at room temperature by using UV-Vis spectroscopy.
Figure 8 shows that spectral changes of the novel ball-type zinc phthalocyanine (2) under the
light irritation. The change of the Q band intensity of the novel ball-type zinc phthalocyanine
with increasing time was recorded. The photodegradation degree of the novel ball-type zinc
phthalocyanines (2) under the light irritation was shown to be insignificant. The
photodegradation quantum yield (Φ
d
) value of the novel ball-type zinc phthalocyanine is
-5
1
.9x10 in DMSO solution. This value is about same with unsubstituted zinc phthalocyanine
-5
(
Φ = 2.6x10 in DMSO). An ideal photosensitizer must be having stable for the use in
d
photodynamic therapy treatment. Thus, the novel ball-type zinc phthalocyanine with 1.9x10-5
photodegradation quantum yield is potential candidate for the photodynamic therapy
treatment of cancer.
4
. Conclusions
We have reported the synthesis of 4,4'-disulfanediyldiphthalonitrile (1) as ligand and their
ball-type zinc phthalocyanine (2). The single crystal X-ray diffraction experiment of the
compound (1) and the Hirshfeld surface analysis has been done in order to reveal the

molecular structure and the bonding dynamics of the supramolecular structure. The structure
of 4,4'-disulfanediyldiphthalonitrile (1) and their ball-type zinc phthalocyanine were
optimized. IR, UV-Vis and NMR spectra of these structures were obtained. These theoretical
spectra were compared with experimental spectra. The data obtained from the theoretical
calculations were in great agreement with the experimental data. The photochemical and
photophysical properties of ball-type zinc phthalocyanines (2) were investigated. The novel
ball type zinc phthalocyanine with 0.89 singlet oxygen quantum yield is potential candidate
for the photodynamic therapy treatment of cancer.
Declaration of interests
The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
Autor statement
Ahmet Turgut BİLGİÇLİ: Investigation, designed, supervised and writing, Hayriye
Genç Bilgiçli:, Investigation, synthesis of compounds, Armağan Günsel: the preparation
of phthalocyanine compounds and their purification, Hasan Pişkin: The analysis of the
single crystal X-ray diffraction data, Burak Tüzün: The performed of quantum chemical
parameters such as HOMO, LUMO, chemical hardness by B3lyp, HF, M062x method, M.
Nilüfer Yarasir: Investigation and characterization, Mustafa Zengin: Investigation,
synthesis and characterization
Acknowledgements
This research were made possible by TUBITAK ULAKBIM, High Performance and Grid
Computing Center (TR-Grid e-Infrastructure) and supported by Research Fund of Sakarya
University (Project Number: : 2018-3-12-195).

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Fig. 1 (a) The asymmetric unit. (b) Atomic arrangement, labels and centre of gravities (Cg)
for the six membered rings. Cg1 and Cg1a represent the gravity centres for the six-
membered rings. Cg2 and Cg2a represent the gravity centres for the five-membered rings.
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representation of the Hirshfeld surface. The black dots indicate the Cg···X (X: S1, N1)
interactions (b) The Olex 2 representation.

Fig.
3
HOMO, LUMO, ESP and the optimized structure of the 4,4'-
disulfanediyldiphthalonitrile (1)
Fig. 4 HOMO, LUMO, ESP and the optimized structure of the studied isomers of the novel
ball type zinc phthalocyanine (2)

Fig. 5 Theoretical and experimental UV-Vis spectrum of the novel ball type zinc
phthalocyanine (2)
Fig. 6 Absorption, excitation and emission spectra of the novel ball type zinc
phthalocyanine (2) in DMSO

Fig. 7 A typical spectrum for the determination of singlet oxygen quantum yield of the
novel ball type zinc phthalocyanine (2) in DMSO
Fig. 8 A typical spectrum for the determination of photodegradation oxygen quantum yield
of the novel ball type zinc phthalocyanine (2) in DMSO.

Scheme 1 The synthesis of the 4,4'-disulfanediyldiphthalonitrile (1)
Scheme 2 The synthesis of the novel ball type zinc phthalocyanine (2)

Table 1 Data collection, refinement parameters and crystallographic information for the
compound (1)
CCDC Number
1912759
Empirical formula
Formula weight (g mol )
Temperature (K)
16 6 4 2
C H N S
318.37
172
-
1
Wavelength (Å)
Mo
Kα
radiation
(
0.71073)
Orthorhombic
P2
Crystal system
Space group
a (Å)
1 1
2 2
12.3002(17)
b (Å)
12.9658(17)
c (Å)
4.7080(6)
α (°)
90
β (°)
90
γ (°)
Volume (Å )
Z
90
3
750.84 (17)
2
Crystal size (mm)
Crystal description
0.494 × 0.177 × 0.086
block, colourless
1.408
-
3
ρ
calcd (g cm )
-
1
μ (mm )
0.354
F(000)
324
θ range for data collection (°)
h, k, l
2.3°–25.1°
-14/14, -15/15, -5/5
10375
1339 (Rint = 0.0594)
1318/0/112
1.120
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R indices [ I > 2σ(I) ]
R
1
=
0.0236,
2
wR =
0
.0642
Largest diff. Peak and hole
0.18 and - 0.19,
RMS 0.04
3
(e Å- )
Table 2 Spectral, photophysical and photochemical properties of the ball-type zinc
phthalocyanine (2)
Stokes shift
-5
Compound

abs, (nm)

Exc (nm)

Ems (nm)

F

d
(10 ) 

∆
(nm)
(
2)
687
-
687
-
699
-
12
0,09
1.9
0,89
-
0,20a
2.61
0,67b
ZnPc
a
b
Data from ref. [55], Data from ref. [68],