Vibrational Spectroscopy 56 (2011) 60–65

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

Effect of pyridine on zinc phthalocyanine studied by density functional theory

calculations and infrared absorption spectroscopy
Sukh Dev Dogra a , Sukhwinder Singh b , Sarvpreet Kaur c , S.K. Tripathi a , G.S.S. Saini a,∗
a
Department of Physics, Panjab University, Chandigarh 160014, India
b
Department of Physics, Government College for Women, Ludhiana, India
c
Department of Physics, Government College for Girls, Sector 11, Chandigarh, India

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

Article history: In the present work, we have studied the effect of pyridine on the zinc phthalocyanine by recording the
Received 12 May 2010 infrared absorption and X-ray diffraction spectra with and without pyridine. In the presence of pyridine
Received in revised form 11 August 2010 phase of the crystalline zinc phthalocyanine changes from ˇ to ˛. Some infrared bands show changes
Accepted 17 August 2010
in their positions and/or intensities. These changes have been interpreted on the basis of coordination
Available online 18 September 2010
of the pyridine molecule with the central zinc ion. Coordinated pyridine transfers some of its charge to
the  electron system of the phthalocyanine ring through zinc ion. Pyridine molecule also distorts the
Keywords:
phthalocyanine molecule by pulling zinc ion out of the phthalocyanine plane. Density functional theory
Zinc phthalocyanine
Phthalocyanine pyridine interaction
also confirms the ligation of pyridine molecule at the fifth coordination site of the central metal ion.
Infrared spectra © 2010 Elsevier B.V. All rights reserved.
X-ray Diffraction
Density functional theory calculations

1. Introduction
Phthalocyanines are well suited for electronic devices due to
their excellent stability against chemicals and temperature, rich
substitution chemistry and processability. Phthalocyanine (Pc) and
its metal analogous (MPc) possess interesting physico-chemical
properties, which have the potential for applications in the area of
non-linear optic, acoustics, gas sensing, magnetic materials, pho-
toconducting agents, photovoltaic cell elements, electrocatalysis,
colorants in chemical industry, optical data storage, photosensi-
tizers, light emitting diodes and dyes [1–7]. In these materials,
excellent chemical tunability of properties can be achieved by
replacing metal ions at the center of the phthalocyanine (Pc)
ring and functionalizing their side groups/axial positions. Zinc
phthalocyanine (ZnPc), complexes have, in particular, been inten-
sively studied due to their excellent photosensitizing properties
[8–11].
It is known that solvents some times leads to the aggregation
of Pcs, which have distinctly different optical properties than the
corresponding monomers [8,12–16]. Solvents also have profound
effects on the crystalline nature of the Pcs and their transformation
from one crystalline form to another is found to increase on the sol-
vent dependent -electron-donating ability of Pcs [17]. Theoretical
∗ Corresponding author. Tel.: +91 172 253 4454; fax: +91 172 278 3336.
E-mail address: gsssaini@pu.ac.in (G.S.S. Saini).
calculations of Caro et al [18] also indicates that solvent plays a role
in stabilization of some Pc molecules, while in others it has a desta-
bilizing effect. However, unsubstituted Pcs are sparsely soluble in
solvents other than pyridine.
Recently, progress has been made towards the understanding
of interaction between Pc and chemical analytes including solvent
vapours at molecular level [19,20] in order to comprehend their
sensing action. It is believed that the electron acceptor molecules
on interaction form charge transfer complex with the Pc molecules
[19]. However, situation is not very clear about the interaction of
Pc with the electron donors. There are some reports which sug-
gest that small amount of charge transfer also takes place in case
of some electron donors such as methanol [20,21]. The purpose
of this work is to elucidate the detailed mechanism of interaction
between ZnPc and pyridine and to investigate the chemical changes
induced by the pyridine at the molecular level. In the present work,
ZnPc, dissolved in pyridine, has been investigated by infrared (IR)
absorption, X-ray diffraction techniques (XRD) and density func-
tional theory (DFT) calculations. Since the wave numbers of infrared
bands are affected by structural changes induced by the interaction,
therefore, study of the effect of pyridine on the infrared frequencies
facilitates the determination of bond lengths changes on a sub-Å
scale. Similar mechanism of pyridine detection may be applicable
to the Pc based sensors in which the pyridine vapour molecules
react with a Pc thin film onto a substrate and provokes a mea-
surable change in a certain property. In recent past, the DFT has
been used to calculate the equilibrium geometries of Pc molecules

0924-2031/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.vibspec.2010.08.010
 S.D. Dogra et al. / Vibrational Spectroscopy 56 (2011) 60–65 61

and their vibrational frequencies [22–24]. Geometry of Pc-vapour Table 1

Calculated average molecular parameters of ZnPc and ZnPc–pyridine complex.
complexes have also been elucidated from DFT [20].
Parameter in Å or degree ZnPc

2. Experimental Free molecule With pyridine

N1–C2 1.37 1.37

ZnPc powder and pyridine from the Aldrich, USA and Quali- N1–C15 1.37 1.37
gens Fine Chemicals, India, respectively, were used without further N1–Zn57 1.99 2.04
C2–N9 1.33 1.33
purification. The solid powder of ZnPc and pyridine product was
C2–C24 1.46 1.46
obtained by a slow evaporation of a saturated solution of ZnPc in C8–N9 1.33 1.33
pyridine at 50–60 ◦ C. The IR spectra of ZnPc and ZnPc–pyridine C15–N16 1.33 1.33
complex in KBr pellets were recorded with a Perkin Elmer PE- C15–C23 1.46 1.46
Rx1 FTIR Spectrophotometer having spectral resolution of 1 cm−1 . C23–C24 1.41 1.41
C23–C33 1.40 1.40
The crystalline phase of the samples were studied by using X-ray C24–C34 1.40 1.40
diffraction technique (Model: Philips X’Pert Pro Multipurpose X-ray C33–C35 1.39 1.39
Diffractometer, Goniometer: PW3050/60, geometry configuration: C33–H49 1.09 1.09
 − , detector: Cu K˛ ). C34–C36 1.39 1.39
C34–H50 1.09 1.09
C35–C36 1.41 1.41
3. Results and discussion C35–H51 1.09 1.09
C36–H52 1.09 1.09
C2–N1–C15 109.4 109.1
3.1. DFT Calculations C2–N1–Zn57 125.3 124.9
C15–N1–Zn57 125.3 125.2
The DFT calculations have been used to investigate the opti- N1–C2–N9 127.5 127.7
N1–C2–C24 108.8 109.1
mized molecular structures of ZnPc and its complex with pyridine.
N9–C2–C24 123.7 123.2
Calculations have been performed with B3LYP functional [25,26] C2–N9–C8 124.3 124.1
and 6-31G(d) basis set using the Gaussian 03 Revision D.01 program N9–C8–C18 123.7 123.2
package [27]. We have also calculated the vibrational frequencies N1–C15–N16 127.5 127.6
of optimized ZnPc and ZnPc–pyridine complex. The attainment of N1–C15–C23 108.8 109.1
N16–C15–C23 123.7 123.2
local minima on the potential energy surface has been confirmed
C15–C23–C24 106.5 106.3
by the absence of imaginary values of vibrational wave numbers. C15–C23–C33 132.4 132.6
The optimized structures of ZnPc and its complex with pyridine are C24–C23–C33 121.1 121.1
depicted in Fig. 1. This figure also shows the atom labeling scheme C2–C24–C23 106.5 106.4
of these molecules. Selected optimized structural parameters of C2–C24–C34 132.4 132.6
C23–C24–C34 121.1 121.1
these molecules are given in Table 1. C23–C33–C35 117.8 117.8
In order to elucidate the zinc phthalocyanine and pyridine inter- C23–C33–H49 120.6 120.6
action, it is assumed that pyridine molecule interacts with the C35–C33–H49 121.6 121.6
central zinc ion at its fifth and/or sixth coordination sites. For opti- C24–C34–C36 117.8 117.8
C24–C34–H50 120.6 120.6
mization of structure of five coordinated ZnPc–pyridine (ZnPcPy)
C–36–C34–H50 121.6 121.6
complex, C2v symmetry constraints have been imposed. Similar C33–C35–C36 121.2 121.1
calculations were performed on six coordinated ZnPc–(pyridine)2 C33–C35–H51 119.6 119.6
(ZnPc(Py)2 ) with and without D2h symmetry constraints. The fre- C36–C35–H51 119.2 119.2
quency analysis has been performed to verify that optimized C34–C36–C35 121.2 121.1
C34–C36–H52 119.6 119.6
structures correspond to minima on the potential energy surface. C35–C36–H52 119.2 119.2
Imaginary frequencies were obtained only for both the possible N1–Zn57–N7 90.0 87.1
structures of ZnPc(Py)2 . Hence, the possibility of formation of six C15–N1–C2–N9 180.0 177.1
coordinated ZnPc(Py)2 can be ruled out. The interaction energy C15–N1–C2–C24 0.0 −1.1
Zn57–N1–C2–N9 0.0 −12.1
(E) of the ZnPc and pyridine molecules has also been calculated.
Zn57–N1–C2–C24 180.0 169.7
The calculated value of E is 17.6 kcal/mol, which suggests moder- C2–N1–C15–C23 0.0 1.1
ate interaction between these molecules. The calculated structures C2–N1–Zn57–C7 0.0 18.2
of ZnPcPy, shown in Fig. 2, represent the interacting molecules N1–C2–N9–C8 0.0 −2.6
in their gas phase. Therefore, the calculated structure of ZnPcPy C24–C2–N9–C8 180.0 175.4
N1–C2–C24–C23 0.0 0.7
may be considered as an approximation for the solid sample. The N1–C2–C24–C34 180.0 180.0
coordination of pyridine molecule at the fifth coordination site of N9–C2–C24–C23 180.0 −177.7
the zinc ion induces structural changes in the ZnPc molecules by N9–C2–C24–C34 0.0 1.6
forcing the zinc ion out of the mean Pc plane. The out-of-plane dis- C15–C23–C24–C2 0.0 0.0
C15–C23–C24–C34 180.0 −179.3
placement of the zinc ion also increases the Zn–Ni bond lengths
C33–C23–C24–C34 0.0 0.0
(Table 1); there is significant deviations in the dihedral angles of C24–C23–C33–C35 0.0 0.4
the Pc molecule. Apart from the displacement of the central ion, Pc C2–C24–C34–C36 180.0 −179.5
molecule is no longer planar, which can also be inferred from the C23–C24–C34–C36 0.0 −0.4
Fig. 2b. The ZnPcPy complex belongs to C2v point group symmetry, C33–C35–C36–C34 0.0 0.0

which can be inferred from the calculated molecular parameters

and Fig. 2c.
Calculated Mulliken charges of ZnPc, and ZnPcPy suggest par-
tial charge transfer between ZnPc and pyridine molecules. Pyridine
coordinated ZnPc has −0.15 units of more Mulliken atomic charge,
compared to free ZnPc. Coordinated pyridine molecule has same
amount of positive charges, suggesting thereby charge transfer
from pyridine molecule to ZnPc molecule on interaction. The charge
transfer may be explained on the basis of lone pair of electron on
nitrogen atom of the pyridine, which transfers some of its elec-
tron density to the ZnPc molecule through the central metal ion.
62 S.D. Dogra et al. / Vibrational Spectroscopy 56 (2011) 60–65

Fig. 1. Structure and atom numbering scheme of (a) zinc phthalocyanine and (b) pyridine.

The calculated charge on the zinc atom in ZnPcPy complex is 0.04
units more positive compared to ZnPc. Similarly, Mulliken atomic
charges on all the 4 inner nitrogen atoms, Ni , have been decreased
on coordination with pyridine. This observation seems to contra-
dict the fact that the pyridine transfers some of its electronic charge
to the ZnPc. However, zinc ion further donates charge to the  elec-
tron system of the ZnPc molecule; similar to the  back donation
observed in the porphyrin molecules, involving electron donor and
metal ion [28]. Further, evidence of the  back bonding is given by
the calculated charges on the carbon atoms marked as Ca , Cb and Cc ,

Fig. 2. Interaction between zinc phthalocyanine and pyridine molecules: (a) free zinc phthalocyanine molecule seen through the molecular plane; (b) zinc
phthalocyanine–pyridine complex seen through the phthalocyanine molecular plane, and (c) zinc phthalocyanine–pyridine complex seen through the pyridine molecular
plane.
 S.D. Dogra et al. / Vibrational Spectroscopy 56 (2011) 60–65 63

100 B1u , B2u , Eg symmetry. The vibrational modes of symmetry species

(a) A2u and Eu are allowed according to the selection rules. Therefore,
spectra of ZnPc show some intense bands assignable to the modes
of Eu and A2u symmetry. Some weak intensity bands are also seen

1269
Transmission (%)

1146
in their spectra. These bands may arise due to the formation of

1216
1482

1067

604
50 aggregates, which are responsible for the relaxation in the selection

1030
992
rules. All the observed bands along with assignments are listed in
Table 2. The table also shows calculated IR frequencies after scal-
1580

748
ing, which has been done with the help of linear fitting (y = mx + c)
1438

with observed frequencies (m = 0.9543 and c = 16.9171 for ZnPc and

0 m = 0.9639 and c = 6.9814 for ZnPcPy). As can be seen from the fig-

705
ure and table, some bands of ZnPc and pyridine either shift or show
change in the intensity for the ZnPcPy complex.
100
(b) In the IR spectrum of ZnPc, we observe intense bands in the
C–H bending region at 727, 752 and 780 cm−1 . These band posi-
tions, therefore, reveal that ZnPc powder has ˇ crystalline phase,
1608

956
1004

571
1453

635

500
1409

since these bands are sensitive to crystal packing arrangements of

1164
Transmission (%)

878
1483

888

Pc and very often these bands are used to identify different crys-
780
1285

50
talline polymorphs ˛, ˇ, ε etc [29]. There exists a strong association
1060

between various molecular stacks inside a ˇ crystalline phthalocya-

1333

752
1088

nine due to close proximity of the  electrons in one molecule and

1103

the peripheral hydrogen atoms of the molecules in adjacent stacks.

This reduces the effective molecular symmetry of ZnPc in solid form
727

0
as a result of which the weak intensity forbidden bands also appear
in its IR spectrum. Observed intensity pattern of the bands at 948
100 and 956 cm−1 also supports the presence of ˇ-crystalline phase of
(c)
ZnPc [29].
1356

800
1218

The C–H bending modes are observed in the IR spectrum of

940
1603

ZnPcPy (Fig. 3) at 720, 750 and 772 cm−1 with a shoulder at

1409

632
1444

772

499
1004

570

779 cm−1 . These band positions except the shoulder match well
Transmission (%)

1164

1038
1282

with the corresponding bands in the IR spectrum of the ˛ crystalline

886

50
1484

form. Therefore, it can be inferred from this observation that the

prepared ZnPcPy sample has predominantly the ˛ form. The pres-
1330

1058
1116

750

ence of the shoulder at 779 cm−1 indicated presence of ˇ crystalline

1089

ZnPc. It is also noteworthy that simultaneous presence of ZnPcPy

720

0 in ˛ and ˇ crystalline phases has already been reported in the lit-

erature [17]. Further evidence of ˇ to ˛ conversion is provided by
the presence of the bands at 867 and 946 cm−1 in the spectrum of
ZnPcPy (Fig. 3c), since bands at these positions in CuPc have already
1650 1450 1250 1050 850 650 450
been assigned to the ˛ crystallites [29].
Wavenumber (cm-1)
The simultaneous presence of ZnPcPy in ˛ and ˇ crystalline
Fig. 3. Infrared absorption spectra of (a) pyridine; (b) zinc phthalocyanine in KBr phases can also be inferred from the XRD spectra depicted in Fig.
pallet; and (c) zinc phthalocyanine–pyridine complex in 450–1700 cm−1 region. 4. Trace a of the figure shows the diffraction pattern of ZnPc and

which show increase in their Mulliken atomic charges on pyridine

coordination.

3.2. IR Spectra

The observed IR spectra of ZnPc in the absence and presence of

Counts/s (arb.)

pyridine in the wave number region 450–1700 cm−1 have been dis-
played in Fig. 3. Trace a of the figure also shows the IR spectrum of
pyridine. In order to simplify the assignment of observed IR bands
of ZnPc, using the fact that this complex in solid form are molec-
ular crystals, the internal vibrations can be considered as those of
a single molecule with slight perturbations from the neighboring b
molecules.
The DFT calculations resulted in the D4h symmetry for this pla-
nar molecule (see Fig. 1a). Moreover, previous DFT calculations
of ZnPc also resulted in the idealized D4h point group symme- a
try [20,24]. Therefore, the following vibrational analysis of ZnPc
5 10 15 20 25 30 35
molecule is based on the D4h point group symmetry. This molecule
2θ (deg)
has 57 atoms and accordingly 165 normal modes of vibrations,
which can be divided into two groups: in-plane vibrations of sym- Fig. 4. Observed X-ray diffraction spectra of (a) zinc phthalocyanine; and (b) zinc
metry A1g , A2g , B1g , B2g , Eu and out-of-plane vibrations of A1u , A2u , phthalocyanine–pyridine complex.
64 S.D. Dogra et al. / Vibrational Spectroscopy 56 (2011) 60–65

Table 2
Position and assignment of observed infrared bands of zinc phthalocyanine, pyridine and their complex.

Infrared bands positions (cm−1 ) Assignment a

ZnPc Pyridine ZnPcPy

Exp. Cal. Cal. Int. b Exp. Exp. Cal. Cal. Int. b

458 p (ring)
500 505 9.46 499 500 10.03 Eu ; ı (iso) +  (Nb –Nb )
571 575 10.53 570 568 9.48 Eu ; ı (iso)as + ı (Nb –Ca –Ni )as
604 628(sh) 627 11.01 ıp (ring)
635 620 0.0 632 631 7.70 Eu ; ı (iso)as + ı (Ca –Nb –Ca )as
651w 649 0.55 ıp (C–C–N)+ıp (C–C–C)
694 684 0.0 683 0.01 ı (iso) + ı (Ca –Nb –Ca )
705 706(sh) 693 21.90 p (C–H)
727 718 146.73 720 732 209.20 A2u ; ı (C–H) + ı (Ca –Nb –Ca ) + ı (Ca –Ni –Ca )
748 p (C–H)
752 750 56.41 750 744 67.09 Eu ; ı (iso)as +  (Ni –Ni ) + ı (Ca –Ni –Ca )as
798 2.29 772 773 22.85  (C–H)
780 798 2.29 779(sh) 791 1.03 A2u ;  (C–H)
800 834 0.0 800(w) A1g ;  (Ni –Ni ) + iso breath + ı (benz)
825w 825 3.55 A1g ;  (Ni –Ni ) + iso breath + ı (benz)
878 873 0.66 867 871 0.09 Eg ;  (C–H)
888 882 38.57 886 879 37.03 Eu ;  (Ni –Ni ) +  (Nb –Nb ) + ı (iso)
948 936 3.06 940 933 2.89 A2u ;  (C–H)
956 966 0.0 946 963 0.00 Eg ;  (C–H)
992 p (ring)
1004 1008 5.85 1004 1007 9.91 Eu ; ı (C–H) +  (Cc –Cc )as + (Cc –Cd )as
1008 0.0 1009(sh) 1007 12.08 A1g ; ı (C–H) +  (Cc –Cc )as + (Cc –Cd )as
1030 1038 1023 9.54 p (ring)
1060 1055 76.68 1058 1054 93.88 Eu ; ı (C–H) + ı (iso) +  (Ni –Ni )
1067 1067 ıp (C–H)
1088 1098 113.26 1089(broad) 1097& 124.52 Eu ; ı (C–H) + ı (Ca –Ni –Ca ) +  (Ni –Ni )
1101 92.96
1103 1107 0.0 1108 0.0 B2g ; ı (C–H) + ı (pyr ring)
1117 1113 186.99 1116 1112 198.52 Eu ; ı (C–H) +  (Ca –Cb )
1146 1152 2.39 ıp (C–H)
1164 1163 65.27 1164 1164 67.08 Eu ; ı (C–H) +  (Ca –Ni )
1173(sh) 1182 4.22 1213 0.06 Eu ; ı (C–H)as +  (Ni –Ni )
1216 1218 1216 18.79 ıp (C–H)
1269 1262 1276 0.01 p (C–N)+p (C–C)+ıp (C–H)
1285 1282 39.18 1282 1283 34.49 Eu ; ı (C–H) +  (Ca –Ni )
1312 1316 25.89 1323 19.18 Eu ; ı (C–H)+ (Ca –Cb )+ (Zn–Ni )+ (Ca –Ni )
1333 1339 243.26 1330 1340 219.98 Eu ; ı (C–H)+ (C–C) benz+ (Zn–Ni )+ (Ca –Nb )as
1341 0.0 1356(w) 1342 5.07 A1g ; ı (C–H)+ (C–C) benz
1409 1405 86.05 1409 1409 70.10 Eu ; ı (C–H)+ (Ca –Cb )+ (C–C) benz+ (Ca –Nb )
1438 1444 1448 16.21 p (C–N)+p (C–C)+ıp (C–H)
1453 1460 35.78 1456 1462 46.66 Eu ; ı (C–H)+ (C–C) benz + (Ca –Nb )
1482 1487 3.15 p (C–N)+p (C–C)+ıp (C–H)
1483 1483 70.93 1484 1488 74.09 Eu ; ı (C–H)+ı (Ca –Ni –Ca )+ (Ca –Nb )
1508 1497 0.0 1508 1501 0.97 A1g ;  (iso)+ı (C–H)+ (Ca –Nb )+ı (Ca –Ni –Ca )
1580 1586 0.52 p (C–C)+ıp (C–H)
1579 8.79 1599(sh) 1586 11.51 Eu ;  (Ca –Nb )+ı (Ca –Ni –Ca )
1608 1603 11.91 1608 1609 11.39 Eu ; ı (C–H) + ı (Cb –Cc ) + ı (Cc –Cd )
a
Subscript p denotes the vibrations related to pyridine. Symbols , ı,  and  denote the stretching, in-plane bending, out-of-plane bending and heaving motion [22],
respectively. Notations iso, as breath, benz and pyr have been used for isoindole, asymmetric vibration, breathing vibration, benzene and pyrrole, respectively.
b
Calculated intensity is given in units of km mol−1 .

all the observed peaks may be assigned to ˇ crystalline ZnPc [17].
Trace b shows additional diffraction peaks, which may arise due to
various planes of the ˛ crystalline ZnPcPy. Some of these additional
peaks at 2 = 7.56, 16.39, 20.67 and 25.50 degree can be assigned to
˛ crystalline phase of ZnPc [17]. Strongest peak in the spectrum of
ZnPcPy (trace b) at 2 = 26.33 degree is also present in the spectrum
of ZnPc (trace a). This peak corresponds to d = 3.38 Å and arises due
to diffraction from the molecular planes stacked along the b-axis
of crystals. The other additional peaks were not assigned due to
non-availability of ICDD cards and X-ray diffraction data of ZnPc to
us.
Apart from the change in the crystalline phase, pyridine interac-
tion also causes change in the position of some other IR bands. For
example, bands at 1285 and 1333 cm−1 shift downward by 3 cm−1
whereas band at 1453 cm−1 shifts upward by 3 cm−1 . Since, posi-
tions of these higher wave number bands are insensitive to the
crystalline phase change, therefore, changes in their positions can
only be explained on the basis of interaction between ZnPc and
pyridine at molecular level. This interaction causes a change in the
conformation of ZnPc molecule as discussed below. Since, pyridine
is well known coordinating solvent, which has also been confirmed
by the DFT calculations, therefore, pyridine molecule interacts with
the phthalocyanine molecule through the fifth coordination site of
the central metal ion. This ligation of pyridine molecule pulls the
zinc ion out of the mean phthalocyanine plane, which has been
confirmed by the DFT calculations (Fig. 2). The out-of-plane dis-
placement of the zinc ion increases the mean separation between
metal and inner nitrogen (Ni ) atoms from 1.99 to 2.04 Å (calcu-
lated). This increased separation and decreased Mulliken atomic
charges on central metal ion and inner nitrogen atoms weaken the
bonding between zinc and Ni atoms. This leads to lowering of the
position of the bands involving primarily the Zn-Ni stretching or
any other vibrations involving the motion of these atoms. On the
other hand band at 1453 cm−1 mainly arises due to the C–C and
 S.D. Dogra et al. / Vibrational Spectroscopy 56 (2011) 60–65
Ca –Nb stretching. Although, the average separation between C–C
and Ca –Nb atoms remains unchanged on pyridine coordination,
yet there is increase in the Mulliken charge on these atoms due
to charge transfer from the pyridine to the  electron systems and
subsequently  back bonding. This may strengthen the bonding
between these atoms and may shift upward the position of band
at 1453 cm−1 . The displacement of the zinc ion from the molecular
plane leads to doming of macrocycle with decrease in overall sym-
metry of the phthalocyanine molecule from D4h to C4v . However, if
the attached pyridine molecule is also taken into account then the
global symmetry of the ZnPcPy molecule can be taken as C2v .
Intensity of some bands has also been altered on pyridine inter-
action. Some new bands have also been observed in the spectrum of
ZnPcPy. For example, weak bands at 825 and 1009 cm−1 are present
in the spectrum of ZnPcPy. These bands have A1g symmetry under
the D4h and, therefore, forbidden for ZnPc. However, due to ligation
of pyridine at the fifth coordination site, the symmetry of ZnPcPy
is reduced to C2v . In this point group, modes of symmetry species
A1g transform to the A1 species, which are allowed according to the
selection rules of IR absorption. Hence, observation of these bands
in the IR spectrum of ZnPcPy further supports the ligation of pyri-
dine molecule at the fifth coordination site of zinc ion. Change in the
intensity of other bands at 1060, 1117 and 1164 cm−1 can also be
explained on the basis of coordination of pyridine with zinc ion. The
calculations of IR frequencies also support the observed intensity
changes in the spectrum of ZnPcPy compared to ZnPc.
One may argue that two pyridine molecules may also simultane-
ously attached to fifth and sixth coordination site of the zinc metal
ion, i.e. formation of ZnPc(Py)2 may take place. In such situation, the
zinc ion remains in the mean phthalocyanine plane with approx-
imate symmetry of the phthalocyanine molecule D4h (if pyridine
molecules are neglected). However, if pyridine molecules are also
taken into account, the overall global symmetry of ZnPc molecule is
reduced to C2v . In this point group, vibrations of A1g type transform
to Ag type, which are still forbidden. Hence, presence of the bands
at 1117 and 1164 cm−1 excludes the possibility of formation of six
coordinated ZnPc(Py)2 complex. Further due to the filled d orbital
of zinc ion, the sixth coordinated ZnPc similar to porphyrins [30] is
unstable at room temperature and has not been reported in the lit-
erature. As discussed in the previous section, DFT calculations also
confirm the instability of ZnPc(Py)2 complex.
4. Conclusions
On the basis of above discussion, it can be concluded that the
pyridine interacts with the central zinc ion and forms a five coor-
dinated zinc phthalocyanine–pyridine complex. Solid ZnPc, which
has ˇ crystalline phase, changes its phase to ˛ on interaction with
pyridine. Ligation of pyridine at the fifth coordination site of the zinc
ion causes shift in the positions of some IR bands by weakening or
strengthening certain bonds due to charge transfer from pyridine
to zinc phthalocyanine molecule. Pyridine molecule also reduces
the molecular symmetry of ZnPc molecule from D4h to C2v by mov-
ing zinc atom out of the phthalocyanine plane, which is responsible
65
for the change in the intensity of some IR bands and observation of
certain new bands. Above conclusion is also supported by the DFT
calculations. The present study may be helpful in understanding
the pyridine sensing mechanism of zinc phthalocyanine.
Acknowledgments
This work is financially supported by the Department of Science
and Technology, India. IR and XRD spectra were recorded at SAIF,
Panjab University.
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