Synthesis and self-assemble nanofibers of tetra phenoxy substituted nickel phthalocyanine

Article abstract of DOI:10.14233/ajchem.2014.17332

Tetra phenoxy substituted nickel phthalocyanine nanofibers were synthesized in large scale by self-assemble. The FESEM and HRTEM micrographs indicated that the sizes of the fibers are 20-60 nm in width and 0.2-5 μm in length. The formation mechanism of ni

Full text of DOI:10.14233/ajchem.2014.17332

Asian Journal of Chemistry; Vol. 26, No. 6 (2014), 1711-1713
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.17332
Synthesis and Self-Assemble Nanofibers of Tetra Phenoxy Substituted Nickel Phthalocyanine†
1
2
2,*
JUNSHAN GAO , GUOQING HUANG and XIGUANG DU
1School of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001, P.R. China
2Faculty of Chemistry, Northeast Normal University, Changchun 130021, P.R. China
*Corresponding author: E-mail: jshgao@aust.edu.cn
Published online: 10 March 2014;
AJC-14873
Tetra phenoxy substituted nickel phthalocyanine nanofibers were synthesized in large scale by self-assemble. The FESEM and HRTEM
micrographs indicated that the sizes of the fibers are 20-60 nm in width and 0.2-5 µm in length. The formation mechanism of nickel
phthalocyanine fibers was discussed and studied by XRD and UV-visible spectra. The nickel phthalocyanine nanofibers have potential
application on organic function devices.
Keywords: Nickel phthalocyanine, Nanofibers, Synthesis, Self-assemble.
CN
INTRODUCTION
OH
CN
CN
LiOH·H2O
O
CN
Phthalocyanines (Pcs) and their derivatives are excellent
organic semiconductors. They have potential applications in
chemical sensors1, nonlinear optics2, photovoltaic cell3 and
field effect transistors4. Recently, one-dimensional nanostruc-
tures of phthalocyanines attract great interest, because of the
larger surface areas which can cause the enhanced optical and
electronic properties. Normally, the one-dimensional nano-
structures of phthalocyanines are prepared under ultrahigh
vacuum atmosphere, such as organic vapor-phase deposition5
or electrochemical methods, such as electrocrystallization6 and
AAO template-based electrophoretic deposition7. But, the
equipments are expensive or the yields are low, which greatly
minimize the applications of phthalocyanines. Therefore,
simple method with high yields is a new focus on the fabri-
cation of 1D nanostructure phthalocyanines. In this paper, a
simple and reproducible solvent diffusion method was applied
for the fabrication of nickel phthalocyanine (NiPc) nanofibers
in large scale.
+
DMSO, 76.1%
NO
2
O
O
N
N
N
N
N
DBU, pentan-1-ol N2
N
N
Ni
NiCl2·6H2O, 140 °C, 49 %
N
O
O
NiPc
Scheme-I: Synthesis and chemical structures of nickel phthalocyanine
Synthesis of nano-fibers of nickel phthalocyanine: The
nickel phthalocyanine molecules could self-assemble to nano-
fibers via a simple solvent diffusion method9. First, methanol
was added dropwise into chloroform solution of nickel phthalo-
cyanine (2.7 mg/mL). Then the nickel phthalocyanine molecules
self-aggregated into fibers. The fibers were washed carefully
by ethanol to remove chloroform. The morphology of the nickel
phthalocyanine fibers were observed by the FESEM (LEO1550)
and HRTEM (FEI-Technai20). The molecular packing of the
EXPERIMENTAL
Synthesis of nickel phthalocyanine: 2,9(10),16(17),23(24)-
Tetra(2-isopropyl-5-methylphenoxy) nickel phthalocyanine
(NiPc) was provided by the Northeast Normal University. The
nickel phthalocyanine was synthesized by phthalonitrile
derivative and NiCl2 according to the literature8, as shown in
Scheme-I.
†Presented at The 7th International Conference on Multi-functional Materials and Applications, held on 22-24 November 2013, Anhui
University of Science & Technology, Huainan, Anhui Province, P.R. China

1712 Gao et al.
Asian J. Chem.
aggregated nickel phthalocyanine was demonstrated by the
XRD (Bruker D-8) and the UV-VIS (Cary-500).
2000
1500
1000
500
0
RESULTS AND DISCUSSION
Morphologies: Fig. 1 shows the typibal FESEM micro-
graph (nickel phthalocyanine-a) and HRTEM micrograph
(nickel phthalocyanine-b) of the nickel phthalocyanine fibers.
Most of the fibers are arranged in nanostructures. The fibers
are 20-60 nm in width and 0.2-5 µm in length. The fibers are
smooth and uniform.
NiPc-a
20
40
2θ (º)
60
80
Fig. 2. XRD pattern the nickel phthalocyanine fibers
a - solution
b - nanofibers
500nm
b
NiPc-b
a
400
600
800 1000 1200 1400 1600 1800 2000
Wavelength (nm)
Fig. 3. UV-VIS absorption spectura of the nickel phthalocyanine solurion
(a) and the fibers (b)
This means that the surrounding conditions of the central Ni
ions are changed in the nanofibers which exclude the formation
of Ni-O coordination bond between the neighboring nickel
phthalocyanine molecules. The Q band absorption is related
to front orbital of the metal-Pc rings, thus this indicates a tight
packing between the nickel phthalocyanine molecules by
strong π-π interaction in the fibers11.
Formation mechanism: The formation of nickel phthalo-
cyanine fibers is embodied in the XRD and UV-visible spectra,
which could be understood by three interactions of the molecules.
First of all, it’s the π-π interaction of the nickel phthalocyanine
molecules that drives to self-assemble and causes the UV-visible
spectra of nickel phthalocyanine nanofibers blue shift compared
with the solution. The second interaction is the π-π interaction
between the benzene rings around nickel phthalocyanine rings.
The third interaction is a coordination of the central Ni ion and
the oxygen atom in the aryloxy group of another molecule11.
100nm
Fig. 1. FESEM micrograph (nickel phthalocyanine-a) and the HRTEM
micrograph (nickel phthalocyanine-b)
XRD: Fig. 2 demonstrates the XRD of nickel phthalo-
cyanine nanofibers as deposited on a quartz substrate at room
temperature. In the XRD spectrum, two clear diffraction peaks
are found at 4.75 and 25.79º, whose plane separations are
approximately 18.6 and 3.5 Å, respectively. The two peaks of
the fibers show that the nickel phthalocyanine molecules have
been arranged in highly long-range ordered lamellar structures
and the two separations are the interlayer spacing of the nano-
fibers10.
UV-visible spectra: Fig. 3 shows the UV-visible absorp-
tion spectra of the nickel phthalocyanine solution (5 × 10-5
mol/L in chloroform) and the fibers. Their UV-visible absorp-
tion spectra exhibit the characteristic B band (250-450 nm)
and Q band (550-750 nm) absorption of the phthalocyanine.
In the region, the two bands are different in shape and shift.
When the nickel phthalocyanine molecules self-aggregated,
the B band and Q band blue shifted. The B band absorption is
related to the front orbital of the central metal in the metal-Pc.
Conclusion
In summary, the nickel phthalocyanine nanofibers have
been successfully achieved by self-assembling via a simple
and reproducible solvent diffusion method. The fibers are
arranged in nanostructures with 20-60 nm in width and 0.2-5
µm in length. Based on the XRD and UV-visible studies, the

Vol. 26, No. 6 (2014)
Synthesis and Self-Assemble Nanofibers of Tetra Phenoxy Substituted Nickel Phthalocyanine 1713
3. H.J. Cui, R.M. Ma, P. Guo, Q. Zeng, G. Liu and X. Zhang, J. Mol.
main interactions to form the nanofibers are considered to be
the π-π interaction of nickel phthalocyanine molecules, the
Ni-O coordination and the π-π interaction between the benzene
rings of the peripheral substitutes, respectively. The nickel
phthalocyanine nanofibers have potential application on
organic function devices.
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ACKNOWLEDGEMENTS
8. C.Y. Ma, D.L. Tian, X.K. Hou, Y.C. Chang, F.D. Cong, H.F. Yu, X.G.
Du and G.T. Du, Synthesis, 741 (2005).
9. C.W. Cheng, J.S. Gao, G.Y. Xu, H. Zhang,Y. Li andY. Luo, J. Nanosci.
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Financial support of this project was provided by Doctor
Foundation of Anhui University of Science and Technology
(2011-11131).
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